WO2014196211A1 - Method for producing unsaturated hydrocarbon using metal-containing zeolite catalyst - Google Patents
Method for producing unsaturated hydrocarbon using metal-containing zeolite catalyst Download PDFInfo
- Publication number
- WO2014196211A1 WO2014196211A1 PCT/JP2014/003044 JP2014003044W WO2014196211A1 WO 2014196211 A1 WO2014196211 A1 WO 2014196211A1 JP 2014003044 W JP2014003044 W JP 2014003044W WO 2014196211 A1 WO2014196211 A1 WO 2014196211A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- catalyst
- intermediate pore
- zeolite
- producing
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 411
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 335
- 239000010457 zeolite Substances 0.000 title claims abstract description 297
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- 239000002184 metal Substances 0.000 title claims abstract description 220
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7276—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B01J37/18—Reducing with gases containing free hydrogen
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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- B01J37/03—Precipitation; Co-precipitation
Definitions
- the present invention relates to a method for producing unsaturated hydrocarbons from a raw material mainly composed of saturated hydrocarbons using a zeolite catalyst.
- Lower olefins such as ethylene, propylene, butene, and butadiene, and monocyclic aromatics such as benzene, toluene, ethylbenzene, and xylenes are important basic chemical raw materials that form the basis of the petrochemical industry. These basic chemical raw materials are mainly produced from naphtha, which is a light fraction of crude oil.
- light naphtha which is a relatively low-boiling component of naphtha
- olefins such as ethylene, propylene, butene and butadiene
- light naphtha which is a relatively low-boiling component of naphtha
- pyrolysis steam cracking
- aromatics such as benzene, toluene, ethylbenzene and xylenes are produced in addition to lower olefins.
- propylene demand growth exceeds ethylene demand growth, and this difference in propylene and ethylene demand growth is expected to further accelerate in the future.
- the lower saturated hydrocarbons which are the main components of naphtha, have low reactivity, so the decomposition temperature of naphtha cracking requires a high temperature of 800 ° C. or higher, and a decomposition temperature range in which an economical yield can be obtained. Is limited.
- the higher the temperature of naphtha cracking the higher the yield of ethylene compared to propylene, and the propylene / ethylene ratio in the product is about 0.6 to 0.7 in the high temperature region of 800 ° C. or higher. Since the propylene / ethylene ratio cannot be changed greatly in this temperature range, it can be said that the selective production of propylene is extremely difficult with the current naphtha crackers.
- Patent Document 1 Compared with the current naphtha cracker, which is an energy-intensive plant, this technology enables reduction of energy consumption and further reduction of carbon dioxide emitted in large quantities due to naphtha decomposition (Non-Patent Document) 1).
- intermediate pore zeolites especially MFI zeolites represented by ZSM5 in particular, have excellent performance in producing lower olefins and aromatic compounds.
- the reaction temperature can be lowered to 700 ° C. or lower, and the propylene selectivity and the propylene / ethylene ratio can be greatly improved.
- the amount of methane that is low in value as a chemical raw material is also suppressed.
- these disclosed technologies are not yet mature enough to replace existing pyrolysis.
- the catalyst life is a big problem common to the reaction process using the zeolite catalyst.
- the severer the reaction conditions the more the catalyst performance is significantly lowered.
- the decrease in the catalyst performance causes problems such as a decrease in the yield of the target product and an increase in the load on the purification process due to a change in the product distribution.
- the decrease in the performance of zeolite catalysts is mainly due to the loss of acid properties due to the elimination of aluminum components in the zeolite crystal skeleton caused by the clogging of carbonaceous deposits called coke and contact with high-temperature steam. .
- zeolite catalysts are characterized by having pores with a clear size derived from the crystal structure, and a shape-selective reaction proceeds at acid points in the pores. For this reason, in particular, if a zeolite catalyst having no 12-membered ring or larger large pores is used, sequential side reactions that lead to coke formation are also limited in the pores due to spatial limitations.
- the activity of the catalyst is generally reduced by coking, but it is known that the addition of an oxidizing gas to the raw material suppresses the formation of coke and extends the catalyst life.
- an oxidizing gas to the raw material suppresses the formation of coke and extends the catalyst life.
- Water vapor, carbon dioxide, or the like is used as the oxidizing gas.
- steam is added to the raw material in processes such as propylene production by propane dehydrogenation using a Pt catalyst (Non-patent Document 3) and styrene production by ethylbenzene dehydrogenation using an Fe catalyst (Non-patent Document 4).
- Pt catalyst propane dehydrogenation using a Pt catalyst
- Fe catalyst Fe catalyst
- water vapor acts as an oxidizing gas under high temperature conditions, and promotes removal of coke and coke precursors by a steam reforming reaction in addition to the main reaction in the catalyst layer, thereby suppressing coking.
- zeolite catalysts generally fall into permanent activity when they come into contact with steam under high temperature conditions. This permanent degradation of activity occurs when the Al—O—Si bond in the zeolite framework is hydrolyzed under high temperature conditions, the Al component is eliminated, and the acid properties disappear. Therefore, in order to use water vapor as an oxidizing gas for a high temperature reaction process using a zeolite catalyst, it is necessary to use a zeolite catalyst that has been subjected to a treatment for improving steam resistance.
- Patent Document 2 An example is disclosed in which a zeolite catalyst with improved steam resistance is used, and steam is added to the raw material to perform catalytic cracking of lower saturated hydrocarbons such as naphtha.
- Patent Document 3 a P, Ca, La-containing ZSM5 catalyst is used, and the n-hexane decomposition reaction is performed continuously for 48 hours or more.
- Patent Document 3 a P, Ca, La-containing ZSM5 catalyst is used, and the n-hexane decomposition reaction is performed continuously for 48 hours or more.
- Patent Documents 4 and 5 examples in which water vapor is added to the raw material to perform catalytic cracking reaction of lower saturated hydrocarbons such as naphtha are disclosed (Patent Documents 4 and 5, Non-Patent Document 5). thinking about real continuous operation is not implemented.
- Non-Patent Document 6 A technique for carrying out catalytic cracking reaction of a lower saturated hydrocarbon such as naphtha under a steam addition condition using a zeolite catalyst to which a metal having activity in a steam reforming reaction is added is disclosed.
- Non-Patent Document 6 ZSM5 added with Ni and Ru having activity in steam reforming reaction is used as a catalyst, and a continuous operation for 10 hours is carried out for light naphtha catalytic cracking reaction under steaming conditions.
- Non-Patent Document 7 naphtha catalytic cracking under steaming conditions is carried out using ZSM5 added with Pd having activity in steam reforming reaction as a catalyst.
- methanol is added to the raw material naphtha in addition to water vapor, and the reaction is carried out at a catalyst layer temperature of 635 ° C., but the maximum conversion rate remains at 52.2% and is sufficient.
- the decomposition reaction cannot proceed.
- Non-Patent Document 5 naphtha catalytic cracking is carried out under steam addition conditions using ZSM5 to which Mo and Ce are added as a catalyst.
- the conversion rate remains at a maximum of 55.3%, and the decomposition reaction cannot be sufficiently progressed.
- the reaction time is as short as 5 hours, and practical continuous operation is not performed in view of practical use.
- Example 11 of Patent Document 4 the catalyst layer is divided into a Pt catalyst as the front stage and a Pr-supported ZSM5 catalyst as the rear stage, and the n-butane catalytic cracking reaction is carried out under the condition of steam addition.
- the Pt catalyst is expected to be difficult to efficiently remove coke and coke precursors deposited on ZSM5.
- coking suppression effects are also known for carbon dioxide. It is believed that the mechanism similar to water vapor promotes removal of coke and coke precursors by dry reforming reaction and suppresses coking. Carbon dioxide gas is known to promote an oxidative dehydrogenation reaction in addition to the dry reforming reaction.
- Examples of the process for adding carbon dioxide gas as an oxidizing gas to a saturated hydrocarbon raw material include benzene production by aromatization reaction of lower saturated hydrocarbons such as methane, ethane, and propane, and lower saturated hydrocarbons such as ethane, propane, and butane.
- Examples include a reaction process using an oxidative dehydrogenation reaction, such as production of lower unsaturated hydrocarbons by dehydrogenation reaction of benzene, and styrene production by ethylbenzene dehydrogenation reaction (Non-patent Document 8).
- Non-Patent Documents 9 and 10 examples (Non-Patent Documents 9 and 10) are disclosed in which a metal-containing zeolite catalyst is suitably used under the condition where carbon dioxide gas is added.
- a metal-containing zeolite catalyst is suitably used under the condition where carbon dioxide gas is added.
- Patent Document 2 describes that carbon dioxide gas may be used as a diluent gas as a mode for carrying out a catalytic cracking process of a lower saturated hydrocarbon such as naphtha using a P-containing zeolite catalyst.
- carbon dioxide gas is described as a gas only for the purpose of diluting the raw material, and is not intended to be used as an oxidizing gas at all. No suppression effect is assumed.
- the prior art document does not disclose an example of catalytic cracking reaction in which carbon dioxide gas is added, and has no idea about the effect of improving the catalyst life by adding carbon dioxide gas with respect to the catalytic cracking process of lower saturated hydrocarbons such as naphtha. It doesn't let you.
- Patent Document 4 discloses a reaction result in which carbon dioxide gas generated by oxidation of a raw material is contained in a product in an n-butane catalytic cracking reaction.
- the effect of carbon dioxide contained in the product on the catalyst life is unclear, and continuous operation under realistic conditions has not been carried out from the viewpoint of practicality and economy.
- metal catalysts are activated by using oxygen ion conductors with high lattice oxygen supply ability such as perovskite oxide and cerium oxide as carriers. Is generally known to improve (for example, Non-Patent Documents 11 to 17).
- oxygen ion conductors with high lattice oxygen supply ability such as perovskite oxide and cerium oxide as carriers.
- lattice oxygen supply ability of the catalyst carrier is used for improving the catalyst life has not been disclosed, focusing on these series of prior arts.
- the present invention provides a method for producing lower olefins using a metal-containing zeolite catalyst, which can continuously give lower olefins in a high yield for a long time by catalytic cracking of lower saturated hydrocarbons such as naphtha. Is an issue.
- the present inventors have used a metal-containing zeolite catalyst having a periodic table group 8 to 10 metal and an intermediate pore zeolite as constituents to solve the above-mentioned problems, and used as a raw material naphtha.
- a metal-containing zeolite catalyst having a periodic table group 8 to 10 metal and an intermediate pore zeolite as constituents to solve the above-mentioned problems, and used as a raw material naphtha.
- the present invention includes the following matters.
- T represents Si atom or Al atom
- O represents oxygen atom
- T represents Si atom or Al atom
- O represents oxygen atom
- T represents Si atom or Al atom
- S oxygen atom
- a metal-containing zeolite catalyst containing pore zeolite (Z1) as a constituent element a raw material (O) and an oxidizing gas (S) whose main components are saturated hydrocarbons having a boiling point of 35 to 180 ° C. at 1 atm.
- S oxidizing gas
- the catalyst temperature when the raw material (O) and the oxidizing gas (S) are brought into contact with the metal-containing zeolite catalyst that is, the reaction temperature in the catalytic cracking reaction of the raw material (O), in other words, the catalytic cracking reaction.
- the ratio (V S / V O ) of the volume (V S ) occupied by the gas of the oxidizing gas (S) to the volume (V O ) occupied by the gas of the raw material (O) is 0 at the temperature of the catalyst layer in FIG.
- the metal-containing zeolite catalyst further includes one or more elements selected from the group consisting of Group 3 elements (Y1) and Table 15 elements (Y2) of the periodic table as constituent elements, Y2) is a method for producing a lower olefin according to any one of [1] to [5], wherein Y2) is one or more elements selected from P, As, Sb and Bi.
- the intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′), and the metal (X) is supported on the intermediate pore zeolite (Z1 ′).
- One or more elements selected from the group consisting of Group 3 elements (Y1) and Periodic table 15 elements (Y2) of the periodic table are further supported on the intermediate pore zeolite (Z1 ′), (Y2) is the method for producing a lower olefin according to [9], which is one or more elements selected from P, As, Sb and Bi.
- the intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′), and a metal-containing zeolite catalyst is used as the oxide (Z2) of the element (Y1).
- the intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′), and the metal-containing zeolite catalyst is used as the oxide (Z2) of the element (Y1).
- the metal-containing zeolite catalyst contains P as an essential element as the element (Y2), and Al supported on the intermediate pore zeolite (Z1 ′) is boehmite, pseudoboehmite, alumina, aluminum salt, and non- [13]
- the composition of Si and Al contained in the intermediate pore zeolite (Z1 ′) is in a range of 30 to 100 in terms of a molar ratio (SiO 2 / Al 2 O 3 ) converted to silica and alumina, and The method for producing a lower olefin according to any one of [13] to [15], wherein the total of Al components contained in the metal-containing zeolite catalyst is in the range of 1 to 10% by mass as Al atoms.
- the intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′), and the metal-containing zeolite catalyst is used as the oxide (Z2) of the element (Y1).
- lower olefins can be continuously produced in a high yield for a long period in the catalytic cracking reaction of lower saturated hydrocarbons such as naphtha.
- the method for producing lower olefins comprises a catalytic cracking reaction using a raw material mainly composed of saturated hydrocarbons having a boiling point in the range of 35 to 180 ° C. at 1 atm using the metal-containing zeolite catalyst.
- lower olefins mainly composed of ethylene and propylene are produced.
- “lower olefin” means an olefin having 2 to 4 carbon atoms
- “main component” means that the total of ethylene and propylene is contained in the lower olefin in an amount of 50% by mass or more.
- the raw material (O), the oxidizing gas (S), the intermediate pore zeolite (Z1), the metal-containing zeolite catalyst, the method for preparing the catalyst, the reaction mode, and the like will be described in detail.
- the raw material mainly composed of saturated hydrocarbons having a boiling point of 1 to 1 atm in the range of 35 to 180 ° C., but mainly aliphatic saturated hydrocarbons and alicyclic hydrocarbons having 3 to 10 carbon atoms.
- Examples include raw materials used as components. Specific examples include light naphtha, heavy naphtha, full-range naphtha, FCC gasoline, and pyrolysis gasoline. Heavy fractions such as vacuum gas oil and residual oil that have been lightened by fluid catalytic cracking in the oil refining process are not covered.
- the main component means 70% by mass or more of saturated hydrocarbons having a boiling point in the range of 35 to 180 ° C. at 1 atm.
- sulfur-containing compounds nitrogen-containing compounds and oxygen-containing compounds are included. Hetero compounds such as compounds may be included.
- sulfur-containing compounds are generally undesirable components for metal-containing catalysts because they become poisoning components of metal catalysts.
- the method for producing lower olefins in the present invention does not particularly affect the catalyst performance.
- a gas such as nitrogen and helium having low reactivity may be supplied into the reactor as necessary.
- the oxidizing gas to be brought into contact with the catalyst layer is not particularly limited, and specific examples include water vapor, carbon dioxide gas, nitrous oxide, air, oxygen, ozone and the like. Among these, water vapor and carbon dioxide can be used particularly preferably.
- the intermediate pore zeolite (Z1) serving as the base of the metal-containing zeolite catalyst according to the present embodiment is composed of 10 tetrahedral-type TO 4 (T represents Si atom or Al atom, and O represents oxygen atom) unit. It is a zeolite having a 10-membered ring structure.
- the pores having a pore diameter in the range of 0.50 to 0.65 nm of the zeolite preferably occupy 10% or more of the total pores derived from the zeolite crystal structure, and occupy a volume of 20% or more. More preferably, it occupies a volume of 50% or more.
- the pore derived from the zeolite crystal structure means a pore having a pore diameter in the range of 0.20 to 1.0 nm.
- the pore diameter of the pores derived from the zeolite crystal structure is calculated from the adsorption / desorption isotherm measured by the nitrogen gas adsorption method using the t-plot method.
- the preferred range of the pore diameter of the pores having a 10-membered ring structure of the intermediate pore zeolite (Z1) is 0.50 to 0.65 nm, but the more preferred range is 0.50 to 0.60 nm.
- the progress of the decomposition reaction may be hindered because saturated hydrocarbons contained in the raw material naphtha fraction are difficult to diffuse into the pores due to spatial limitations.
- the progress of coke generation reaction in the pores may be promoted.
- the catalytic cracking reaction of saturated hydrocarbons such as naphtha is sufficient. Can not be controlled.
- the crystal structure of the intermediate pore zeolite (Z1) is preferably MFI type, MWW type or FER type, more preferably MFI type or MWW type, and particularly preferably MFI type.
- an intermediate pore zeolite having an MFI type, MWW type or FER type crystal structure may be referred to as an intermediate pore zeolite (Z1 ').
- the content ratio of silicon element (Si) and aluminum element (Al) contained in the intermediate pore zeolite (Z1) is preferably in the range of 25 to 1000 in terms of SiO 2 / Al 2 O 3 molar ratio, A range of 25 to 300 is more preferable.
- the intermediate pore zeolite (Z1) may be produced by a conventionally known method, or a commercially available product may be used. Examples of commercially available products include NH 4 + type ZSM5 (Zeolyst International).
- the particle size of the intermediate pore zeolite is preferably 10 nm to 5000 nm, more preferably 50 nm to 1000 nm.
- the intermediate pore zeolite (Z1) may be used after being subjected to silylation treatment as necessary in order to cover the acid sites existing on the outer surface of the pores that promote non-selective reactions such as coke formation. .
- silylation treatment There is no restriction
- alkoxysilanes such as tetramethoxysilane, tetraethoxysilane and aminopropyltriethoxysilane; hydrosilanes such as trimethoxysilane, triethoxysilane, 1,3,5,7-tetramethylcyclotetrasiloxane; Silazanes such as hexamethyldisilazane and nonamethyltrisilazane; silicates such as sodium silicate and potassium silicate; and silicon halide compounds such as ammonium hexafluorosilicate, silicon tetrachloride and chlorotrimethylsilane Processing.
- the intermediate pore zeolite (Z1) may be used after subjecting to dealumination as necessary in order to control the acid amount.
- the metal-containing zeolite catalyst according to the present embodiment is a catalyst containing the above-mentioned intermediate pore zeolite (Z1) and periodic table group 8-10 metal (X) as constituent elements.
- the metal-containing zeolite catalyst exhibits an effect as long as it contains one or more types of metal (X), but may be composed of two or more types of metal (X).
- the metal (X) is preferably selected from Ru, Rh, Ir, Ni, Pd and Pt, more preferably selected from Ru, Rh, Ir, Pd and Pt, and Ru, Rh, Pd and Pt. More preferably, it is chosen from.
- examples of two or more types of metal (X) include a combination of Pt and Pd, a combination of Pd and Ru, a combination of Pt and Ru, and the like, but are not limited thereto.
- the content of the metal (X), which is a constituent element of the metal-containing zeolite catalyst, is not particularly limited, but is preferably 0.01 to 30% by mass as an element, and 0.01 to 3% by mass More preferred is 0.01 to 1% by mass, and most preferred is 0.05 to 1% by mass.
- the metal (X) as a component of a metal containing zeolite catalyst.
- Any compound containing at least one of the metals in groups 8 to 10 of the periodic table may contain other elements at the same time. May be.
- Examples of combinations of metals in Group 8 to 10 of the periodic table and other elements include platinum-tin combinations, platinum-indium combinations, platinum-zinc combinations as disclosed in Catalyst Preparation Example 11 described later, and platinum-germanium. Combinations, platinum-tin-indium combinations, platinum-palladium-tin combinations, palladium-tin combinations, palladium-zinc combinations, palladium-indium combinations, palladium-germanium combinations, palladium-ruthenium combinations, etc. Can be raised.
- the content of the other metal relative to the Group 8-10 metal of the periodic table is usually 0.1 to 2.0, preferably as an atomic ratio. Is in the range of 0.3 to 1.5. In general, it is considered that these plural kinds of metals are in an alloy state on the support.
- the scientific form of the metal (X) is a metal ion include platinum (II) ion exchange zeolite, palladium (II) ion exchange zeolite, and the like.
- the intermediate pore zeolite (Z1) constituting the metal-containing zeolite catalyst is preferably an intermediate pore zeolite (Z1 ') having a crystal structure of MFI type, MWW type or FER type.
- the metal-containing zeolite catalyst contains one or more elements selected from the group 3 element (Y1) and the group 15 element (Y2) of the periodic table as a constituent element.
- it contains one or more elements selected from Group 3 element (Y1) of the periodic table and Group 15 element (Y2) of the periodic table as a constituent element, more preferably Group 3 element (Y1) of the periodic table And one or more elements selected from Group 15 element (Y2) of the periodic table as constituent elements.
- one or more elements selected from Group 3 element (Y1) of the periodic table and Group 15 element (Y2) of the periodic table may be collectively referred to as element (Y).
- element (Y) group 3 element (Y1) of the periodic table
- Ce is most preferable.
- P, As, Sb and Bi are preferable as the group 15 element (Y2) of the periodic table, and P is most preferable.
- the content of the element (Y) is not particularly limited, but a preferable composition is as follows.
- the concentration of the total of all Group 3 elements contained in the catalyst is preferably 0.01 to 50% by mass, and preferably 0.01 to 10% by mass. Is more preferably 0.01 to 3% by mass, and most preferably 0.05 to 1% by mass.
- the concentration of the total of all group 15 elements contained in the catalyst is preferably 0.01 to 30% by mass, and preferably 0.01 to 10% by mass. More preferably, the content is 0.01 to 5% by mass, still more preferably 0.05 to 5% by mass.
- the metal-containing zeolite catalyst contains the element (Y) as a constituent element
- the chemical form of the element (Y) there is no particular limitation on the chemical form of the element (Y).
- simple substance, oxide, sulfide, nitride, carbide, boride, halide, hydride, aqua acid, aqua acid salt, aqua acid ion, hydroxo acid, hydroxo acid salt, hydroxo acid ion, oxo Examples include acids, oxoacid salts, oxoacid ions, metal ions and the like.
- the chemical form of each element may be different, but may be a composite form such as a composite oxide.
- the combination of the metal (X) and the element (Y) [(X), (Y)] is not particularly limited. [(X), (Y1)] and [(X), (Y1), (Y2)] can be mentioned. More specifically, [(X), (Y1)] includes [(Pt; Pd), (Ce)], [(Pd), (Ce)], [(Pd; Ru), (Ce).
- [(X), (Y1), (Y2)] include [(Pt), (Ce), (P)], [(Pt; Pd), (Ce), (P )], [(Pd), (Ce), (P)], [(Pd; Ru), (Ce), (P)] and the like.
- [(Pt), (Ce), (P)], [(Pd), (Ce)], [(Pd), (Ce), (P)], [(Pd; Ru), (Ce), (P)] and the like.
- [(Pt), (Ce), (P)]] [(Pd), (Ce), (P)]
- [(Pd; Pd) indicates any of Pt alone, Pd alone, or a mixture of Pt and Pd.
- the content of the metal (X) and the element (Y) is not particularly limited, but examples of the preferred content include the following.
- [(X), (Y1), (Y2)] is [(Pt), (Ce), (P)]
- the Pt content is 0.01 to 3% by mass
- the Ce content is 0.01 to 3% by mass
- P content is preferably 0.1 to 3% by mass
- Pt content is 0.05 to 1% by mass
- Ce content is 0.05 to 1% by mass.
- % And P content is more preferably 0.1 to 3% by mass.
- the content of Pt is 0.01 to 3 mass% and the content of Pd
- the amount is 0.01 to 3% by mass
- the Ce content is 0.01 to 10% by mass
- the P content is 0.1 to 3% by mass
- the Pt content is 0.05 to 3% by mass. More preferably, the content is 1% by mass
- the Pd content is 0.05 to 1% by mass
- the Ce content is 0.05 to 1% by mass
- the P content is 0.1 to 3% by mass.
- the metal-containing zeolite catalyst when the metal-containing zeolite catalyst contains a group 15 element (Y2) in the periodic table, the metal-containing zeolite catalyst preferably contains Al at the same time.
- the total of the Al components contained in the catalyst is preferably 1 to 10% by mass, more preferably 1 to 5% by mass as the total amount with the Al atoms inherent in the zeolite.
- the composition of Si and Al contained in the intermediate pore zeolite (Z1) constituting the catalyst is in the range of 30 to 100 in terms of a molar ratio (SiO 2 / Al 2 O 3 ) converted to silica and alumina. Is preferred.
- the composition of P and Al contained in the catalyst is 0.1 to 1.0 in terms of atomic molar ratio (P / Al). A range is preferable.
- the metal-containing zeolite catalyst may contain an alkali metal (W) in addition to the metal (X) and the element (Y).
- alkali metal (W) include Li, Na, K, Rb, and Cs.
- the amount of (W) is not particularly limited, but the molar ratio (W / Al) to Al in the intermediate pore zeolite (Z1) is 0.001 to 0.5. A range is preferable. If the molar ratio (W / Al) is less than 0.001, the acid amount of the intermediate pore zeolite (Z1) cannot be controlled, and cannot contribute to the suppression of sequential side reactions. On the other hand, when the molar ratio (W / Al) exceeds 0.5, the acid amount of the intermediate pore zeolite (Z1) is decreased and the activity may be excessively lowered.
- the amount of the strong acid point of the metal-containing zeolite catalyst is not particularly limited, but is preferably in the range of 10 to 1500 ⁇ mol per 1 g of the metal-containing zeolite.
- the amount of strong acid point is evaluated by the ammonia temperature programmed desorption method (NH 3 -TPD).
- NH 3 -TPD measurement results are plotted with the temperature desorption curve plotted with the horizontal axis as the desorption temperature and the vertical axis as the ammonia gas desorption amount as the acid intensity distribution, and 250 ° C. to 800 ° C. on the temperature desorption curve. Only the acid point group corresponding to the peak appearing in the range of is quantified as a strong acid point.
- the form of the metal-containing zeolite catalyst is not particularly limited, and may be used as a catalyst as a powder, but may be used as a molded catalyst with a binder added as necessary.
- a molding catalyst an agglomerate obtained by pressurizing and compressing the powder catalyst, a compression molded product obtained by crushing the agglomerate to an appropriate particle size, and a tableting in which the powder catalyst is compressed and solidified into a certain shape by a tableting machine. Examples include, but are not limited to, a molded body, an extruded molded body obtained by extruding a kneaded material prepared by adding a binder, a thickening stabilizer, water, and the like to a powder catalyst through a mold.
- Method for preparing metal-containing zeolite catalyst As long as the metal-containing zeolite catalyst according to the present invention satisfies the above-described properties, there is no particular limitation on the method for preparing the catalyst.
- the method for preparing the catalyst according to the present invention is roughly divided into the following methods (1), (2) and (3).
- a part of the metal (X) may be supported on the intermediate pore zeolite (Z1 ′).
- (Z1 ′), (Z2) or (Z3) may be referred to as “carrier”.
- the catalyst obtained by the method (1) may be called a single carrier type catalyst, and the catalyst obtained by the method (2) or the method (3) may be called a multiple carrier type catalyst.
- a catalyst is preferable, and a metal-containing zeolite catalyst in which the metal (X), the element (Y1), and the element (Y2) are both supported on the intermediate pore zeolite (Z1 ′) is more preferable.
- Examples of the oxide (Z2) of the element (Y1) used in the method (2) or the method (3) include cerium (IV) oxide, lanthanum oxide, and aluminum-cerium composite oxide.
- the inorganic solid compound (Z3) used in the method (2) or the method (3) includes perovskite compounds such as strontium titanate, lanthanum manganate, LaFe 0.57 Co 0.38 Pd 0.05 O 3 and the like. Phosphates such as aluminum phosphates, cerium phosphates and lanthanum phosphates; and silica, alumina, boehmite, pseudoboehmite, zirconium oxide, titanium oxide, magnesium oxide, amorphous silica-alumina, carbon, carbonized Silicon etc. are mentioned.
- the oxide (Z2) of the element (Y1) and the inorganic solid compound (Z3) in the method (2) and the method (3) may be used also as a binder at the time of molding.
- the lattice oxygen can promote the catalytic effect of the metal (X) on the reforming reaction by the oxidizing gas.
- a carrier having a high supply ability include perovskite compounds such as strontium titanate and lanthanum manganate, cerium oxide (IV), aluminum-cerium composite oxide, and the like.
- Cerium (IV) oxide as the oxide (Z2) of the element (Y1) and a perovskite compound as the inorganic solid compound (Z3) are preferable.
- the amount of the element (Y1) oxide (Z2) used is not particularly limited, but in order to reduce the influence on the catalytic cracking reaction of lower saturated hydrocarbons, the intermediate pore zeolite (Z1) is added to 100 parts by mass. On the other hand, the range is preferably from 0.1 to 20 parts by mass, more preferably from 1 to 10 parts by mass.
- the aluminum-containing compound (A) is added to the mesoporous zeolite (Z1) because the lower olefins are provided in a high yield over a long period of time.
- Preferred addition forms of the aluminum-containing compound (A) include a form in which the aluminum-containing compound (A) is further supported on the intermediate pore zeolite (Z1) in addition to the element (Y2), or an oxide (Z2) or an inorganic solid compound Examples include (Z3) a form using an aluminum-containing compound (A).
- the amount of the aluminum-containing compound (A) added is preferably in the range of 1 to 10% by mass, more preferably in the range of 1 to 5% by mass, with the total of the aluminum components contained in the metal-containing zeolite catalyst being Al atoms.
- the aluminum-containing compound (A) is not particularly limited as long as it is a substance not corresponding to the intermediate pore zeolite (Z1), but at least selected from boehmite, pseudoboehmite, alumina, aluminum salt, and amorphous silica-alumina.
- One aluminum-containing compound is preferably used, and more preferably at least one compound selected from boehmite and pseudoboehmite.
- the present inventor has confirmed that the effect of the present embodiment is exhibited if the aluminum-containing compound (A) is supported on the intermediate pore zeolite (Z1) even in a small amount.
- the element (Y2) is preferably phosphorus (P).
- the “physical mixture” means one prepared by a physical mixing method. Examples of the “physical mixing method” include physical mixing methods (a) to (e) described below.
- a solution containing a desired amount of metal (X), element (Y) and other elements in the form of a simple substance or a compound is prepared, and intermediate pore zeolite (Z1), oxide of element (Y1) (Z2)
- the impregnation method in contact with the inorganic solid compound (Z3), the metal (X), the element (Y) and other elements are vaporized in the form of a simple substance or a compound to form a gas of the intermediate pore zeolite (Z1) or the element (Y1).
- a vapor deposition method for contacting with an oxide (Z2) or an inorganic solid compound (Z3) is known.
- the impregnation method includes pore filling method, incipient wetness method, equilibrium adsorption method, evaporation to dryness method, spray drying method, deposition method, and ion exchange method. Examples include chemical vapor deposition and physical vapor deposition.
- a preferred method is an impregnation method that is relatively easy to operate and does not require special equipment.
- the metal (X) when the metal (X) is Pd, palladium oxide (II), palladium acetate (II), palladium chloride (II), palladium nitrate (II), tetraammine palladium (II)
- the metal (X) is Pt, such as chloride, tetraamminepalladium (II) nitrate, etc., platinum (IV) oxide, platinum (IV) chloride, tetraammineplatinum (II) chloride, platinum (II), platinum chloride (IV ), Etc.
- the metal (X) is Ir, hexachloroiridium (IV) acid, oxidized (IV) iridium, iridium chloride (III), iridium chloride (IV), etc.
- the metal (X) is Ru, ruthenium chloride ( III), ruthenium oxide (IV), ruthenium oxide (VIII), potassium hexachlororuthen
- any available compound such as a simple metal, an alloy, an oxide, a sulfide, a nitride, a carbide, a boride, an acid and a salt can be used. it can.
- the element (Y1) is Ce, cerium (III) oxide, cerium (IV) oxide, cerium (III) acetate, cerium (III) nitrate, cerium (III) chloride, cerium (III) carbonate, etc.
- the element (Y2) is P
- orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, pyrophosphoric acid, diammonium hydrogen phosphate and the like can be mentioned.
- the form of the solution in the case where it is necessary to prepare a solution containing the metal (X), the element group (Y), and other element materials
- a solution in which the raw material is dissolved in a solvent a colloidal solution or a suspension in which the raw material is uniformly dispersed in the solvent, a slurry solution in which the raw material is dispersed in the solvent but settled when left standing, and the like And the like.
- a solution containing a plurality of raw materials among the raw materials of metal (X), element (Y), and other elements may be prepared.
- the solvent that dissolves or disperses the raw materials of the metal (X), the element (Y), and other elements.
- the solvent that dissolves or disperses the raw materials of the metal (X), the element (Y), and other elements.
- water hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid and other water-soluble solvents, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol and other alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
- Ketones diethyl ether, dimethyl ether, tetrahydrofuran, ethers such as 1,3-dioxane, 1,4-dioxane, esters such as ethyl acetate and propyl acetate, dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, halogenated hydrocarbons such as orthodichlorobenzene, aromatic hydrocarbons such as benzene, toluene, xylenes, mesitylene, tetralin, acetonitrile, dimethyl Sulfoxide, dimethyl Le formamide, and mixtures thereof.
- ethers such as 1,3-dioxane, 1,4-dioxane, esters such as ethyl acetate and propyl acetate, dichloromethane, chloro
- the solution containing the raw material of the metal (X) may be used for supporting by the impregnation method as it is.
- the metal (X) may be subjected to a liquid phase reduction treatment in a solution and used as a colloidal solution containing the metal (X).
- the liquid phase reduction method is not particularly limited, and the solution containing the metal (X) raw material includes hydrosilanes such as triethylsilane, carboxylic acids such as citric acid, sodium citrate, ascorbic acid, sodium borohydride, Examples thereof include a method of adding a reducing agent such as hydrazine and heating as necessary, a method of preparing a solution containing a reducing solvent such as alcohols and heating as necessary. Moreover, when performing a liquid phase reduction process, you may add protective agents, such as polyvinylpyrrolidone, dodecane thiol, sodium polyacrylate, methylcellulose, polyethyleneglycol, as needed.
- protective agents such as polyvinylpyrrolidone, dodecane thiol, sodium polyacrylate, methylcellulose, polyethyleneglycol, as needed.
- the support supporting the metal (X), the element (Y) and other elements may be used as it is as a catalyst or for catalyst preparation by physical mixing with other components. You may use after performing a process and both the processes.
- a firing treatment at 250 to 800 ° C. in air, more preferably 350 to 600 ° C. in air, and particularly preferably 450 to 550 ° C. in air is preferable.
- a reduction process Specifically, a hydrogen atmosphere process, a reducing agent solution spraying process, etc. are mentioned.
- the hydrogen atmosphere treatment is performed by heating as necessary in a hydrogen gas atmosphere diluted with hydrogen gas or inert gas.
- the reducing agent solution spray treatment is a solution in which a reducing agent such as hydrosilanes such as triethylsilane, carboxylic acids such as citric acid, sodium citrate, and ascorbic acid, sodium borohydride, hydrazine, etc. is dissolved in an appropriate solvent as necessary. And sprayed or dropped on the support.
- a reducing agent such as hydrosilanes such as triethylsilane, carboxylic acids such as citric acid, sodium citrate, and ascorbic acid, sodium borohydride, hydrazine, etc.
- each component is sequentially deposited in a fixed bed reactor to form a catalyst layer composed of a plurality of layers.
- the methods (a), (b), (c) and (e) are more preferable, and the methods (a) and (b) are most preferable.
- distributes the raw material of a metal (X), an element (Y), and another element is mentioned. .
- the catalyst physically mixed by the above method may be used as a catalyst as it is, or may be used after performing a calcination treatment, a reduction treatment, and both treatments.
- a firing treatment at 250 to 800 ° C. in air, more preferably 350 to 600 ° C. in air, and particularly preferably 450 to 550 ° C. in air is preferable.
- a reduction process Specifically, a hydrogen atmosphere process, a reducing agent solution spraying process, etc. are mentioned.
- the hydrogen atmosphere treatment is performed by heating as necessary in a hydrogen gas atmosphere diluted with hydrogen gas or inert gas.
- the reducing agent solution spray treatment is a solution in which a reducing agent such as hydrosilanes such as triethylsilane, carboxylic acids such as citric acid, sodium citrate and ascorbic acid, sodium borohydride and hydrazine is dissolved in an appropriate solvent as necessary. It is carried out by spraying or dripping onto the support.
- a reducing agent such as hydrosilanes such as triethylsilane, carboxylic acids such as citric acid, sodium citrate and ascorbic acid, sodium borohydride and hydrazine
- the reaction mode for carrying out the production method of the present invention is not particularly limited, such as a fixed bed type, a fluidized bed type, and a moving bed type, but a fixed bed type that can be easily replaced with the current naphtha steam cracking is preferable.
- the metal-containing zeolite catalyst used for the reaction may be pretreated before the reaction, if necessary.
- the pretreatment is as follows: (1) high temperature treatment with inert gas such as nitrogen and helium for the purpose of removing the adsorbed material on the catalyst surface, and (2) reduction of metal components of the catalyst. And high-temperature reduction treatment while circulating hydrogen or diluted hydrogen.
- inert gas such as nitrogen and helium
- high-temperature reduction treatment while circulating hydrogen or diluted hydrogen.
- the oxidizing gas can be brought into contact with the catalyst layer by being generated as a result of the reaction in the catalyst layer, but it is desirable to supply at least a part of the oxidizing gas to the catalyst layer after mixing with the raw material.
- the source gas and the oxidizing gas may be supplied continuously or discontinuously.
- a method may be used in which the supply of the source gas is temporarily stopped, only the oxidizing gas is supplied to the catalyst layer, and the source gas is supplied again to the catalyst layer. Examples of the method for supplying gas discontinuously include a first method and a second method described below.
- the supply of the raw material gas is temporarily stopped to supply the oxidizing gas to the catalyst layer, and then the raw material is again supplied.
- gas is supplied to the catalyst layer.
- the second method is a method in which only the source gas is supplied to the catalyst layer, the supply of the source gas is temporarily stopped to supply the oxidizing gas, and then the source gas is supplied again to the catalyst layer. It is.
- the source gas may be supplied together with the oxidizing gas or only the source gas may be supplied.
- reaction temperature Since the catalytic cracking reaction is generally endothermic, the higher the reaction temperature, the more thermodynamically advantageous the reaction proceeds. However, the high temperatures of 800 ° C. and higher, which are commonly used in naphtha pyrolysis, are severe conditions for zeolite catalysts. Yes, the activity decreases in a short time. On the other hand, it is necessary to carry out the reaction at a high temperature that does not interfere with the production of unsaturated hydrocarbons and that allows removal of coke and coke precursors with an oxidizing gas. From these restrictions, the temperature of the catalyst layer in the catalytic cracking reaction is preferably in the range of 500 to 750 ° C., more preferably in the range of 600 to 700 ° C.
- the reaction temperature in the catalytic cracking reaction of lower saturated hydrocarbons such as naphtha of the present invention is the temperature of the catalyst layer, and the temperature of the catalyst layer means the average temperature of the entire catalyst layer.
- the temperature of the catalyst layer means the average temperature of the entire catalyst layer.
- it is heated from the outside, it is greatly deviated from the average temperature of the entire catalyst layer in the vicinity of the reactor wall where the temperature is locally high, or the location where the temperature is particularly low due to the influence of the endotherm due to the decomposition reaction. There is a case. Therefore, in order to measure the average temperature of the entire catalyst layer, it is necessary to select and measure a location that is not a special environment.
- the temperatures of both ends and the center of the catalyst layer in the axial direction of the catalyst layer are measured in the vicinity of the center of the cross section of the reaction tube, and the average of three temperatures The method of taking.
- reaction pressure In the production method of the present invention, since the conversion of saturated hydrocarbons to unsaturated hydrocarbons is a decomposition reaction, it can be said that the progress of the reaction becomes thermodynamically disadvantageous as the partial pressure of the raw material increases. On the other hand, it is not preferable from the viewpoint of economy that the partial pressure of the raw material is too low. For this reason, the partial pressure of the raw material (when the raw material is a mixture, the total partial pressure of all reaction products) is preferably in the range of 0.01 to 0.20 MPa. The total pressure in the reactor is not particularly limited but is preferably in the range of 0.1 to 1.0 MPa.
- V O is preferably in the range of 0.01 to 2, more preferably in the range of 0.01 to 1, and most preferably in the range of 0.1 to 1.
- V O is calculated assuming that the average molecular weight is 86, which is the same as the molecular weight of n-hexane, and both V O and V S are in contact with the catalyst layer. It shall be calculated as the volume of the gas before
- the contact time of the grade which does not produce coking so that reaction fully advances and reaction progress is not preferable.
- the weight hourly space velocity (WHSV) per mass of the intermediate pore zeolite (Z1) component defined by the following formula (1) is in the range of 0.1 to 30 h ⁇ 1 , More preferably, it is carried out in the range of ⁇ 15 h ⁇ 1 .
- WHSV [h ⁇ 1 ]) (raw material supply amount [g / h]) / (mass of intermediate pore zeolite (Z1) component [g]) (1)
- An intermediate pore zeolite SiO 2 / Al 2 O 3 molar ratio NH 4 + type MFI zeolite (Zeolyst International) was calcined in air at 500 ° C. for 4 hours to obtain SiO 2 / Al 2 O 3.
- a H + type MFI zeolite catalyst (H-ZSM5) with a molar ratio of 30 was prepared.
- H—ZSM5 (10 g) having a SiO 2 / Al 2 O 3 molar ratio of 30 was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure.
- P / ZSM5 (2.5 g) and 0.24 g of Pd / CeO 2 were sufficiently physically mixed using a mortar as powder to prepare Pd / CeO 2 + P / ZSM5.
- the resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator.
- the residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Ni / CeO 2 containing 330 ⁇ mol of Ni per 1.0 g of cerium (IV) oxide.
- Pd / CeAlO 3 + P / ZSM5 was prepared by sufficiently physically mixing P / ZSM5 (2.5 g) and Pd / CeAlO 3 0.24 g in a powder using a mortar.
- P / ZSM5 2.5 g
- 0.24 g of Pd / LaMnO 3 were sufficiently physically mixed using a mortar as powder to prepare Pd / LaMnO 3 + P / ZSM5.
- Example 1 Activity evaluation: synthetic naphtha decomposition reaction n-pentane 29% by mass, n-hexane 14% by mass, 2-methylpentane 14% by mass, n-octane 29% by mass, methylcyclohexane 7% by mass, cyclohexane 7
- the reagent was mixed so that it might become the mass%, and the liquid fully stirred was used as the synthetic naphtha.
- the Ru / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 1 was pressed and compressed to form agglomerates.
- the agglomerates were crushed and sized to a particle size of 0.25 mm to 0.50 mm and fixed.
- the activity was evaluated by a synthetic naphtha decomposition reaction using a bed flow reactor.
- the reaction tube was filled with 0.86 g of Ru / CeO 2 + P / ZSM5 as a catalyst, and the temperature was raised to 600 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 600 ° C., reduction treatment was performed for 1 hour while flowing hydrogen through the reactor at a flow rate of 50 Ncc / min.
- the flow gas was switched from hydrogen to nitrogen, pretreatment was performed for 1.5 hours while flowing in the reactor at a flow rate of 50 Ncc / min, and the temperature was raised to 650 ° C. of the reaction temperature.
- the nitrogen circulated in the reaction tube was stopped, and instead the raw material synthetic naphtha was pressurized at a flow rate of 7.5 g / h and steam at a flow rate of 0.75 g / h so that the total pressure was 0.15 MPa.
- the WHSV per mass of the intermediate pore zeolite is 10 h ⁇ 1
- the volume ratio V S / V O of the synthetic naphtha gas which is the raw material at the reaction temperature and the water vapor which is the oxidizing gas is 0.48
- the synthesis The reaction was started under the condition that the partial pressure of naphtha gas was 0.10 MPa.
- the reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- Example 2 The activity of the Pd / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 2 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Pd / CeO 2 + P / ZSM5 was charged as a catalyst. .
- Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- Example 3 For the Pd / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 2, the mass of intermediate pore zeolite was the same as in Example 1 except that the water vapor supply rate was 3.8 g / h and the total pressure was 0.35 MPa. The activity was evaluated by a synthetic naphtha decomposition reaction under the conditions of a per unit WHSV of 10 h ⁇ 1 and a V S / V O of 2.4. Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- Example 4 The activity of the Ni / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 3 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Ni / CeO 2 + P / ZSM5 was charged as a catalyst. .
- Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- Example 5 The activity of the Pd / CeAlO 3 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 4 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Pd / CeAlO 3 + P / ZSM5 was charged as a catalyst. . Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- Example 6 The activity of the Pd / LaMnO 3 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 5 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Pd / LaMnO 3 + P / ZSM5 was charged as a catalyst. . Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- H-ZSM5 catalyst with a SiO 2 / Al 2 O 3 molar ratio of 500 pressurize and compress to form agglomerates, crush the agglomerates and adjust the particle size to 0.25 mm to 0.50 mm and fix
- the activity was evaluated by a synthetic naphtha decomposition reaction using a bed flow reactor.
- the reaction tube was filled with 0.75 g of H 2 -ZSM5 having a SiO 2 / Al 2 O 3 molar ratio of 500 as a catalyst, and the reaction temperature was 650 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. The temperature was raised to.
- the nitrogen circulated in the reaction tube was stopped, and instead, the raw material synthetic naphtha was pressurized to a total pressure of 0.10 MPa at a flow rate of 7.5 g / h and supplied to the reaction tube.
- WHSV per pore zeolite mass is 10 h ⁇ 1
- volume ratio V S / V O of synthetic naphtha gas as raw material and water vapor as oxidizing gas at reaction temperature is 0, and partial pressure of synthetic naphtha gas is 0.11 MPa
- the reaction was started.
- the reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- WHSV per pore zeolite mass is 10 h ⁇ 1
- volume ratio V S / V O of synthetic naphtha gas as raw material and water vapor as oxidizing gas at reaction temperature is 0, and partial pressure of synthetic naphtha gas is 0.11 MPa
- the reaction was started.
- the reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 1 shows the yield of each product calculated based on the mass of the carbon component.
- the metal-containing zeolite catalyst containing Pd or Ru is excellent in both catalyst performance and catalyst life when used under the steam addition reaction conditions, and in particular, when used under conditions where V S / V O is 2.0 or less. It has been found that it is excellent, especially in the case of a metal-containing zeolite containing Ce as a constituent element.
- Catalyst Preparation Example 6 Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + Al-P / ZSM5) Boehmite (manufactured by Wako Pure Chemical Industries, Ltd.) 0.67 g and diammonium hydrogen phosphate (Wako Pure Chemical Industries, Ltd.) in 100 ml of distilled water H-ZSM5 (10 g) having a SiO 2 / Al 2 O 3 molar ratio of 30 prepared in Catalyst Preparation Example 1 was added to the mixed solution obtained by adding 1.7 g and stirring at room temperature, and stirring at room temperature. did. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C.
- Al—P / ZSM5 was prepared by steam treatment.
- Catalyst Preparation Example 7 Preparation of metal-containing zeolite catalyst (Ru / CeO 2 + Al-P / ZSM5) Instead of 0.23 g of Pd / CeO 2, 0.23 g of Ru / CeO 2 prepared in Catalyst Preparation Example 1 was used. Ru / CeO 2 + Al—P / ZSM5 was prepared in the same manner as in Catalyst Preparation Example 6 except that
- Al—P / ZSM5 (2.7 g) prepared in Catalyst Preparation Example 6 and 0.23 g of Pd—Pt / CeO 2 were sufficiently physically mixed using a mortar in the form of powder, and Pd—Pt / CeO 2 + Al— P / ZSM5 was prepared.
- Example 7 Activity evaluation: n-hexane decomposition reaction
- the Pd / CeO 2 + Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 6 was pressed and compressed into aggregates, and the aggregates were crushed. The particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor.
- the reaction tube was filled with Pd / CeO 2 + Al—P / ZSM5 (0.94 g) as a catalyst, and the temperature was raised to 400 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure.
- WHSV per mass of intermediate pore zeolite is 10 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 0.48
- n The reaction was started under the condition that the partial pressure of hexane gas was 0.068 MPa.
- the reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 2 shows the yield of each product calculated based on the mass of the carbon component.
- Example 8 In the same manner as in Example 7, except that the Ru / CeO 2 + Al—P / ZSM5 catalyst prepared in Catalyst Preparation Example 7 was charged with 0.94 g of Ru / CeO 2 + Al—P / ZSM5 as a catalyst, n-hexane The activity was evaluated by a decomposition reaction. Table 2 shows the yield of each product calculated based on the mass of the carbon component.
- Example 9 The Pd—Pt / CeO 2 + Al—P / ZSM5 catalyst prepared in Catalyst Preparation Example 8 was the same as in Example 7 except that 0.94 g of Pd—Pt / CeO 2 + Al—P / ZSM5 was charged as a catalyst. The activity was evaluated by n-hexane decomposition reaction. Table 2 shows the yield of each product calculated based on the mass of the carbon component.
- the nitrogen flowing through the reaction tube was stopped, and instead, the reaction was carried out so that the total pressure became 0.10 MPa at a flow rate of 7.5 g / h for raw material n-hexane and 0.75 g / h for water vapor.
- WHSV per mass of intermediate pore zeolite is 10 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 0.48, n
- the reaction was started under the condition that the partial pressure of hexane gas was 0.068 MPa.
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 2 shows the yield of each product calculated based on the mass of the carbon component.
- the metal-containing zeolite catalyst containing Pd, Ru, or a Pd—Pt mixture as the metal (X) under the condition of steam addition is superior in both catalyst performance and catalyst life compared to the zeolite catalyst not containing the metal (X). It became clear that it was excellent.
- Pd—Ru / CeO 2 + Al—P / ZSM5 was prepared in the same manner as in Catalyst Preparation Example 6 except that 0.23 g of Pd—Ru / CeO 2 was used instead of 0.23 g of Pd / CeO 2 .
- Example 10 Activity evaluation: n-hexane decomposition reaction For the Pd-Ru / CeO 2 + Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 9, 0 was used as the catalyst for Pd-Ru / CeO 2 + Al-P / ZSM5. The activity was evaluated by n-hexane decomposition reaction in the same manner as in Example 7 except that .94 g was charged. Table 3 shows the yield of each product calculated based on the mass of the carbon component.
- Example 11 Al-P / ZSM5 prepared in Catalyst Preparation Example 6 and Pd-Ru / CeO 2 prepared in Catalyst Preparation Example 9 were separately pressed and compressed into aggregates, and the aggregates were crushed to 0.25 mm. The particle size was adjusted to a particle size of ⁇ 0.50 mm.
- the sized Al—P / ZSM5 (0.87 g) is first charged into the reaction tube, and then 0.075 g of sized Pd—Ru / CeO 2 is added to the Pd—Ru / CeO 2 layer and The Al—P / ZSM5 catalyst layers were allowed to coexist as individual layers, and the raw materials were arranged so as to contact the Pd—Ru / CeO 2 layer and the Al—P / ZSM5 layer in this order.
- the activity was evaluated by n-hexane decomposition reaction in the same manner as in Example 7. Table 3 shows the yield of each product calculated based on the mass of the carbon component.
- Catalyst Preparation Example 10 Preparation of Metal-Containing Zeolite Catalyst (Pt—Ce / Al—P / ZSM5) With respect to Al—P / ZSM5 (2.0 g) prepared in Catalyst Preparation Example 6, the supported amount of Pt was Pt. Platinum chloride (IV) acid hexahydrate and cerium (III) nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) so that 0.50 mass% as atoms and the supported amount of Ce as 0.30 mass% as Ce atoms Kogyo Kogyo Co., Ltd.) was supported by an incipient wetness method using a solution in which an appropriate amount of distilled water was dissolved.
- Platinum chloride (IV) acid hexahydrate and cerium (III) nitrate hexahydrate so that 0.50 mass% as atoms and the supported amount of Ce as 0.30 mass% as Ce atoms Kogyo Kogyo Co.
- Example 12 Activity evaluation: n-hexane decomposition reaction
- the Pt-Ce / Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 10 was pressed and compressed into aggregates, and the aggregates were crushed. The particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor.
- the reaction tube was filled with 0.91 g of Pt—Ce / Al—P / ZSM5 as a catalyst and heated to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor at atmospheric pressure.
- the nitrogen flowing through the reaction tube was stopped, and instead, the total pressure was 0.10 MPa at a flow rate of raw material n-hexane of 7.5 g / h and water vapor of 2.3 g / h.
- WHSV per mass of intermediate pore zeolite is 10 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and water vapor as the oxidizing gas is 1.4 at the reaction temperature
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 4 shows the yield of each product calculated based on the mass of the carbon component.
- Example 13 Activity Evaluation: n-Hexane Decomposition Reaction
- the Pd / CeO 2 + Al—P / ZSM5 catalyst prepared in Catalyst Preparation Example 6 was pressed and compressed into aggregates, and the aggregates were crushed. The particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor.
- the reaction tube was filled with Pd / CeO 2 + Al—P / ZSM5 (2.4 g) as a catalyst, and the temperature was raised to 400 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure.
- WHSV per mass of intermediate pore zeolite supplied to the reaction tube is 4.0 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 1. 9.
- the reaction was started under the condition that the partial pressure of n-hexane gas was 0.034 MPa.
- the reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 4 shows the yield of each product calculated based on the mass of the carbon component.
- the nitrogen flowing through the reaction tube was stopped, and instead, the reaction was carried out so that the total pressure became 0.10 MPa at a flow rate of 7.5 g / h of raw material n-hexane and 3.0 g / h of water vapor.
- WHSV per mass of intermediate pore zeolite is 4.0 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 1.9 at the reaction temperature.
- the reaction was started under the condition that the partial pressure of n-hexane gas was 0.034 MPa.
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 4 shows the yield of each product calculated based on the mass of the carbon component.
- Example of Pt-Ce / Al-P / ZSM5 catalyst containing Pt as metal (X) for n-hexane decomposition reaction under conditions where water vapor was added so that V S / V O 1.4
- the result of No. 12 was higher in ethylene + propylene yield at 9 hours and 17 hours from the start of the reaction.
- a Pd / CeO 2 + Al—P / ZSM5 catalyst containing Pd as the metal (X) is used.
- the results of Example 13 were compared with the results of Comparative Example 6 using an Al—P / ZSM5 catalyst containing no metal (X), and the ethylene + propylene yield was 1 hour, 11 hours and 27 hours from the start of the reaction. Both were high.
- the supported amount of Pt is 0.50% by mass as Pt atoms
- the supported amount of Zn is 0.30% by mass as Zn atoms. So as to be supported by an incipient wetness method using a solution obtained by dissolving platinum chloride (IV) acid hexahydrate and zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in an appropriate amount of distilled water. did.
- Example 14 Activity Evaluation: n-Hexane Decomposition Reaction
- the P / Pt—Zn / ZSM5 catalyst prepared in Catalyst Preparation Example 11 was pressed and compressed to form aggregates, and the aggregates were crushed to 0.
- the particle size was adjusted to 25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow reactor.
- the reaction tube was filled with P / Pt—Zn / ZSM5 (1.1 g) as a catalyst, and the temperature was raised to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor under atmospheric pressure.
- the nitrogen flowing through the reaction tube was stopped, and instead, the reaction was carried out so that the total pressure became 0.10 MPa at a flow rate of 7.5 g / h for raw material n-hexane and 0.75 g / h for water vapor.
- WHSV per mass of intermediate pore zeolite is 6.8 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 0.48 at the reaction temperature.
- the reaction was started under the condition that the partial pressure of n-hexane gas was 0.068 MPa.
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 5 shows the yield of each product calculated based on the mass of the carbon component.
- H-ZSM5 (2.0 g) having an SiO 2 / Al 2 O 3 molar ratio of 61 prepared in Catalyst Preparation Example 11 was impregnated with 0.087 g of 85% phosphoric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.). After drying, P / ZSM5 was prepared by calcining in air at 650 ° C. for 10 hours. The obtained powder was pressed and compressed into aggregates, and the aggregates were crushed and sized to a particle size of 0.25 mm to 0.50 mm and used for the reaction.
- the prepared SiO 2 / Al 2 O 3 molar ratio 61 / P / ZSM5 was evaluated by n-hexane decomposition reaction in the same manner as in Example 14 except that P / ZSM5 (1.1 g) was charged as a catalyst.
- Table 5 shows the yield of each product calculated based on the mass of the carbon component.
- the resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. After drying the residue after evaporation to dryness, and calcined for 4 hours at 500 ° C. in air, it was prepared of Pd / Al 2 O 3 containing Pd of Al 2 O 3 1.0 g per 330Myumol.
- H-ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of Pd / Al 2 O 3 were sufficiently physically mixed using a mortar as a powder, Pd / Al 2 O 3 + H—ZSM5 was prepared.
- the resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator.
- the residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd / SiO 2 containing 330 ⁇ mol of Pd per 1.0 g of SiO 2 .
- H—ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of Pd / SiO 2 were sufficiently physically mixed using a mortar in the form of Pd / SiO 2 + H—ZSM5 was prepared.
- the resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. After drying the residue after evaporation to dryness, and calcined for 4 hours at 500 ° C. in air, the Pd / La 2 O 3 containing Pd of La 2 O 3 1.0 g per 330 ⁇ mol was prepared.
- H—ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of Pd / La 2 O 3 were sufficiently physically mixed using a mortar, Pd / La 2 O 3 + H—ZSM5 was prepared.
- H-ZSM5 (2.5 g) having a molar ratio of SiO 2 / Al 2 O 3 of 500 prepared in Comparative Example 1 and 0.25 g of Pd / ZrO 2 were sufficiently physically mixed using a mortar in the form of Pd / ZrO 2 + H-ZSM5 was prepared.
- Catalyst Preparation Example 17 Preparation of metal-containing zeolite catalyst (Pd / SrTiO 3 + H-ZSM5) 10 g of strontium carbonate (manufactured by Wako Pure Chemical Industries) and 5.4 g of titanium (IV) oxide (manufactured by Soekawa Riken) The mixture was sufficiently physically mixed using a mortar and fired at 1150 ° C. in air for 10 hours to prepare SrTiO 3 .
- H—ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of Pd / SrTiO 3 were sufficiently physically mixed using a mortar as powder, and Pd / SrTiO 3 + H-ZSM5 was prepared.
- Example 15 Activity Evaluation: n-Hexane Decomposition Reaction
- the Ru / ZSM5 catalyst prepared in Catalyst Preparation Example 12 was pressed and compressed into aggregates, which were crushed and 0.25 mm to 0. The particle size was adjusted to 50 mm and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow reactor.
- the reaction tube was charged with 0.75 g of Ru / ZSM5 as a catalyst, and the temperature was raised to 650 ° C. of the reaction temperature while flowing nitrogen through the reactor under atmospheric pressure.
- the nitrogen flowing through the reaction tube is stopped, and instead the raw material n-hexane is 7.5 g / h and carbon dioxide is 1.9 g / h, so that the total pressure becomes 0.17 MPa.
- the WHSV per mass of intermediate pore zeolite is 10 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and the carbon dioxide gas as the oxidizing gas at the reaction temperature is The reaction was started under the conditions of 0.50 and a partial pressure of n-hexane gas of 0.11 MPa.
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- Example 16 The Pd / Al 2 O 3 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 13 was treated in the same manner as in Example 15 except that 0.83 g of Pd / Al 2 O 3 + H—ZSM5 was charged as a catalyst. The activity was evaluated by a decomposition reaction. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- Example 17 The Pd / SiO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 14 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / SiO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- Example 18 The Pd / La 2 O 3 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 15 was treated in the same manner as in Example 15 except that 0.83 g of Pd / La 2 O 3 + H—ZSM5 was charged as a catalyst. The activity was evaluated by a decomposition reaction. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- Example 19 The Pd / ZrO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 16 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / ZrO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- Example 20 The Pd / SrTiO 3 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 17 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / SrTiO 3 + H—ZSM5 was charged as a catalyst. evaluated. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- Comparative Example 8 The H—ZSM5 catalyst having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 was pressed and compressed into aggregates, and the aggregates were crushed to obtain a particle diameter of 0.25 mm to 0.50 mm. And the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was charged with 0.75 g of H-ZSM5 as a catalyst and heated to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor at atmospheric pressure.
- the nitrogen flowing through the reaction tube was stopped, and instead, the raw material n-hexane was pressurized to a total pressure of 0.11 MPa at a flow rate of 7.5 g / h and supplied to the reaction tube.
- WHSV per mass of intermediate pore zeolite is 10 h ⁇ 1
- volume ratio V S / V O of n-hexane gas as raw material and carbon dioxide gas as oxidizing gas at reaction temperature is 0, and fraction of n-hexane gas
- the reaction was started under the condition of a pressure of 0.11 MPa.
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- Comparative Example 10 The H—ZSM5 catalyst having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 was pressed and compressed into aggregates, and the aggregates were crushed to obtain a particle diameter of 0.25 mm to 0.50 mm. And the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was charged with 0.75 g of H-ZSM5 as a catalyst and heated to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor at atmospheric pressure.
- the nitrogen flowing through the reaction tube is stopped, and instead the raw material n-hexane is 7.5 g / h and carbon dioxide is 1.9 g / h, so that the total pressure becomes 0.17 MPa.
- the WHSV per mass of intermediate pore zeolite is 10 h ⁇ 1
- the volume ratio V S / V O of the raw material n-hexane gas and the carbon dioxide gas as the oxidizing gas at the reaction temperature is The reaction was started under the conditions of 0.50 and a partial pressure of n-hexane gas of 0.11 MPa.
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- the activity of the prepared CeO 2 + H—ZSM5 catalyst was evaluated by n-hexane decomposition reaction in the same manner as in Comparative Example 10 except that 0.83 g of CeO 2 + H—ZSM5 was charged as a catalyst.
- Table 6 shows the yield of each product calculated based on the mass of the carbon component.
- the results of Examples 15 to 20 in which the n-hexane decomposition reaction was carried out under the carbon dioxide addition conditions using the metal-containing zeolite catalyst containing Pd or Ru as the constituent elements were the results of the n-hexane decomposition reaction under the carbon dioxide gas addition conditions.
- the results of Examples 15 to 20 include the results of Comparative Example 10 in which an n-hexane decomposition reaction was performed under the carbon dioxide gas addition conditions using a catalyst not containing metal (X) as a constituent element, and Ce.
- H—ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of the prepared Pd / CeO 2 were sufficiently physically mixed using a mortar as a powder, Pd / CeO 2 + H—ZSM5 containing 6.6 ⁇ mol of Pd per 1.0 g of zeolite was prepared.
- H—ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of the prepared Pd / CeO 2 were sufficiently physically mixed using a mortar as a powder, Pd / CeO 2 + H—ZSM5 containing 66 ⁇ mol of Pd per 1.0 g of zeolite was prepared.
- H—ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of the prepared Rh / CeO 2 were sufficiently physically mixed using a mortar as a powder, Rh / CeO 2 + H-ZSM5 containing 33 ⁇ mol Rh per 1.0 g zeolite was prepared.
- Catalyst Preparation Example 23 Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + Ru / ZSM5) Ru / ZSM5 (2.5 g) prepared in Catalyst Preparation Example 12 and Pd / CeO 2 prepared in Catalyst Preparation Example 2 25 g of the powder was sufficiently physically mixed using a mortar to prepare Pd / CeO 2 + Ru / ZSM5 containing 33 ⁇ mol of Pd and 33 ⁇ mol of Ru per 1.0 g of zeolite.
- Example 21 Example 15 except that Pd / CeO 2 + H—ZSM5 catalyst containing 6.6 ⁇ mol of Pd per 1.0 g of the zeolite prepared in Catalyst Preparation Example 18 was charged with 0.83 g of Pd / CeO 2 + H—ZSM5 as a catalyst. In the same manner as described above, the activity was evaluated by n-hexane decomposition reaction. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
- Example 22 A Pd / CeO 2 + H—ZSM5 catalyst containing 33 ⁇ mol of Pd per 1.0 g of the zeolite prepared in Catalyst Preparation Example 19 was the same as Example 15 except that 0.83 g of Pd / CeO 2 + H—ZSM5 was charged as a catalyst. Then, the activity was evaluated by n-hexane decomposition reaction. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
- Example 23 A Pd / CeO 2 + H—ZSM5 catalyst containing 66 ⁇ mol of Pd per 1.0 g of the zeolite prepared in Catalyst Preparation Example 20 was the same as Example 15 except that 0.83 g of Pd / CeO 2 + H—ZSM5 was charged as a catalyst. Then, the activity was evaluated by n-hexane decomposition reaction. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
- Example 24 The Ru / CeO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 21 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Ru / CeO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
- Example 25 The Rh / CeO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 22 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Rh / CeO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
- Example 26 The Pd / CeO 2 + Ru / ZSM5 catalyst prepared in Catalyst Preparation Example 23 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / CeO 2 + Ru / ZSM5 was charged as a catalyst. evaluated. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
- the results of Examples 21 to 26 using the catalyst containing the metal (X) and Ce as the constituent elements show that the constituent element contains Ce but the metal (X) Compared to the results of Comparative Example 11 in Table 6 using a catalyst containing no catalyst and the results of Examples 15 to 20 in Table 6 using a catalyst containing metal (X) but not containing Ce as a constituent element
- the ethylene + propylene yield was high at 1 hour, 22 hours and 37 hours. That is, the metal-containing zeolite catalyst containing Pd, Ru or Rh as the metal (X) is excellent in both catalyst performance and catalyst life when used under carbon dioxide addition reaction conditions, and further, Ce is used as the element group (Y). It became clear that it was superior when contained.
- Catalyst Preparation Example 24 Preparation of Metal-Containing Zeolite Catalyst (Pd / CeO 2 + P / Pt—Ce / ZSM5) H-ZSM5 (2.0 g) having a SiO 2 / Al 2 O 3 molar ratio of 50 prepared in Catalyst Preparation Example 11 ) Platinum chloride (IV) acid hexahydrate and cerium nitrate so that the supported amount of Pt is 0.50% by mass as Pt atoms and the supported amount of Ce is 0.30% by mass as Ce atoms.
- the obtained Pt—Ce / ZSM5 was impregnated with 0.087 g of 85% phosphoric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), dried and then calcined in air at 650 ° C. for 10 hours to obtain P / Pt—Ce / ZSM5.
- 0.087 g of 85% phosphoric acid aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.
- P / Pt—Ce / ZSM5 (2.0 g) and 0.19 g of Pd / CeO 2 prepared in Catalyst Preparation Example 2 were sufficiently physically mixed using a mortar as a powder, and Pd / CeO 2 + P / Pt ⁇ Ce / ZSM5 was prepared.
- Example 27 Activity Evaluation: n-Hexane Decomposition Reaction
- the Pd / CeO 2 + P / Pt—Ce / ZSM5 catalyst prepared in Catalyst Preparation Example 24 was pressed and compressed into aggregates, and the aggregates were crushed Then, the particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor.
- the reaction tube was filled with 1.8 g of Pd / CeO 2 + P / Pt—Ce / ZSM5 as a catalyst, and the temperature was raised to 600 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure.
- WHSV per mass of intermediate pore zeolite is 5.0 h ⁇ 1
- the volume ratio V S / V O of n-hexane gas as a raw material and carbon dioxide gas as an oxidizing gas at the reaction temperature is The reaction was started under the condition that the partial pressure of the 2.0, n-hexane gas was 0.037 MPa.
- the reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 8 shows the yield of each product calculated based on the mass of the carbon component.
- Example 28 For the Pd / CeO 2 + P / Pt—Ce / ZSM5 catalyst prepared in Catalyst Preparation Example 24, the same procedure as in Example 27 was performed except that the carbon dioxide supply rate was 11 g / h and the total pressure was 0.11 MPa. The activity was evaluated by n-hexane decomposition reaction under the conditions of WHSV per pore zeolite mass of 10 h ⁇ 1 , V S / V O of 3.0, and partial pressure of n-hexane gas of 0.028 MPa. Table 8 shows the yield of each product calculated based on the mass of the carbon component.
- the nitrogen flowing through the reaction tube is stopped, and instead the raw material n-hexane is 7.5 g / h and carbon dioxide gas is 7.7 g / h so that the total pressure becomes 0.11 MPa.
- WHSV per mass of intermediate pore zeolite is 5.0 h ⁇ 1
- V S / V O of n-hexane gas as a raw material and carbon dioxide gas as an oxidizing gas at the reaction temperature is The reaction was started under the condition that the partial pressure of the 2.0, n-hexane gas was 0.037 MPa.
- reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed.
- Table 8 shows the yield of each product calculated based on the mass of the carbon component.
- Comparative Example 14 For the H—ZSM5 catalyst having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1, the same procedure as in Comparative Example 13 was conducted except that the carbon dioxide supply rate was 11 g / h and the total pressure was 0.11 MPa. The activity was evaluated by n-hexane decomposition reaction under the conditions of WHSV per mesopore zeolite mass of 5 h -1 and V S / V O of 3.0. Table 8 shows the yield of each product calculated based on the mass of the carbon component.
- S / V O 3.0
- the ethylene + propylene yields at 1 hour, 22 hours and 37 hours were all high.
- T represents Si atom or Al atom
- O represents oxygen atom
- Z1 intermediate pore zeolite
- Catalyst temperature when the raw material (O) and the oxidizing gas (S) are contacted with the metal-containing zeolite catalyst that is, the reaction temperature in the catalytic cracking reaction of the raw material (O), in other words, contact Ratio (V S / V O ) of the volume (V S ) occupied by the gas of the oxidizing gas (S) to the volume (V O ) occupied by the gas of the raw material (O) at the temperature of the catalyst layer in the decomposition reaction
- V S / V O contact Ratio of the volume (V S ) occupied by the gas of the oxidizing gas (S) to the volume (V O ) occupied by the gas of the raw material (O) at the temperature of the catalyst layer in the decomposition reaction
- the metal-containing zeolite catalyst further contains one or more elements selected from the group consisting of Group 3 elements (Y1) and Periodic table 15 elements (Y2) as a constituent element,
- Y1 Group 3 elements
- Y2 Periodic table 15 elements
- the intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′), and the metal (X) is added to the intermediate pore zeolite (Z1 ′).
- the intermediate pore zeolite (Z1 ′) further carries one or more elements selected from the group consisting of Group 3 elements (Y1) and Table 15 elements (Y2) of the Periodic Table, The method for producing a lower olefin according to [2-9], wherein the element (Y2) is one or more elements selected from P, As, Sb and Bi.
- the metal-containing zeolite catalyst contains the element (Y1), and the intermediate pore zeolite (Z1) is an MFI-type, MWW-type, or FER-type intermediate pore zeolite (Z1 ′), and contains a metal [2-6] wherein the zeolite catalyst is a physical mixture of the metal (X) supported on the oxide (Z2) of the element (Y1) and the intermediate pore zeolite (Z1 ′).
- the metal-containing zeolite catalyst contains the element (Y1) and the element (Y2), and the intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′
- the metal-containing zeolite catalyst is supported on the metal (X) supported on the oxide (Z2) of the element (Y1) and the intermediate pore zeolite (Z1) supported on the element (Y2).
- the metal-containing zeolite catalyst contains P as an essential element as the element (Y2), and Al supported on the intermediate pore zeolite (Z1 ′) is boehmite, pseudoboehmite, alumina, aluminum salt, And a process for producing a lower olefin according to [2-13] derived from at least one aluminum-containing compound (A) selected from amorphous silica-alumina.
- the composition of Si and Al contained in the intermediate pore zeolite (Z1 ′) is in the range of 30 to 100 in terms of a molar ratio (SiO 2 / Al 2 O 3 ) converted to silica and alumina,
- composition of P and Al contained in the metal-containing zeolite catalyst is in the range of 0.1 to 1.0 in terms of atomic molar ratio (P / Al) [2-14] to [2-16 ]
- the manufacturing method of the lower olefins in any one of.
- the metal-containing zeolite catalyst contains the element (Y1), and the intermediate pore zeolite (Z1) is an MFI-type, MWW-type, or FER-type intermediate pore zeolite (Z1 ′), and contains a metal Physical mixing of the metal (X) supported on the oxide (Z2) of the element (Y1) and the metal (X) supported on the intermediate pore zeolite (Z1 ′) by the zeolite catalyst The process for producing a lower olefin according to [2-6].
- a metal-containing zeolite catalyst is supported on an inorganic solid compound (Z3) different from both the intermediate pore zeolite (Z1 ′) and the oxide (Z2) of the group 3 element (Y1) of the periodic table.
- Z3 inorganic solid compound
- Z2 oxide
- Y1 group 3 element
- a metal-containing zeolite catalyst is supported on an inorganic solid compound (Z3) different from both the intermediate pore zeolite (Z1 ′) and the oxide (Z2) of group 3 element (Y1) of the periodic table.
- Z3 inorganic solid compound
- Z2-5 which is a physical mixture of the metal (X) and the intermediate pore zeolite (Z1 ′) on which the group 15 element (Y2) of the periodic table is supported Production method.
- a metal-containing zeolite catalyst is supported on an inorganic solid compound (Z3) different from both the intermediate pore zeolite (Z1 ′) and the oxide (Z2) of the group 3 element (Y1) of the periodic table.
- Z3 inorganic solid compound
- Z2-5 The method for producing a lower olefin according to [2-5], which is a physical mixture of the metal (X) and the intermediate pore zeolite (Z1 ′).
- the present invention can be used in a method for producing unsaturated hydrocarbons using a metal-containing zeolite catalyst.
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Abstract
Description
1気圧での沸点が35~180℃の範囲にある飽和炭化水素類を主成分とする原料として特に制限は無いが、炭素数3~10の脂肪族飽和炭化水素および脂環式炭化水素を主成分とする原料等が挙げられる。具体的には、ライトナフサ、ヘビーナフサ、フルレンジナフサ、FCCガソリンおよび熱分解ガソリンなどが挙げられる。なお、石油精製プロセスにおいて流動接触分解により軽質化されている減圧軽油や残油等の重質留分は対象とならない。ここで、主成分とは1気圧での沸点が35~180℃の範囲にある飽和炭化水素類を70質量%以上含んでいることをいい、これ以外に含硫黄化合物、含窒素化合物および含酸素化合物などのヘテロ化合物が含まれていてもよい。特に含硫黄化合物については、一般的に金属触媒の被毒成分となるため金属含有触媒に対しては好ましくない成分とされている。しかしながら、本発明における低級オレフィン類の製造方法においては触媒性能に特に影響を及ぼさない。後述する接触分解の際には、上記原料以外に、必要に応じて反応性の低い窒素およびヘリウム等の気体を反応器内に供給してもよい。 〔material〕
There is no particular limitation on the raw material mainly composed of saturated hydrocarbons having a boiling point of 1 to 1 atm in the range of 35 to 180 ° C., but mainly aliphatic saturated hydrocarbons and alicyclic hydrocarbons having 3 to 10 carbon atoms. Examples include raw materials used as components. Specific examples include light naphtha, heavy naphtha, full-range naphtha, FCC gasoline, and pyrolysis gasoline. Heavy fractions such as vacuum gas oil and residual oil that have been lightened by fluid catalytic cracking in the oil refining process are not covered. Here, the main component means 70% by mass or more of saturated hydrocarbons having a boiling point in the range of 35 to 180 ° C. at 1 atm. In addition, sulfur-containing compounds, nitrogen-containing compounds and oxygen-containing compounds are included. Hetero compounds such as compounds may be included. In particular, sulfur-containing compounds are generally undesirable components for metal-containing catalysts because they become poisoning components of metal catalysts. However, the method for producing lower olefins in the present invention does not particularly affect the catalyst performance. In the catalytic cracking described later, in addition to the above raw materials, a gas such as nitrogen and helium having low reactivity may be supplied into the reactor as necessary.
ナフサ等低級飽和炭化水素の接触分解反応において、触媒層に接触させる酸化性ガスとして特に制限は無いが、具体的には水蒸気、炭酸ガス、亜酸化窒素、空気、酸素、オゾンなどが挙げられる。中でも、水蒸気および炭酸ガスを特に好適に用いることができる。 [Oxidizing gas]
In the catalytic cracking reaction of lower saturated hydrocarbons such as naphtha, the oxidizing gas to be brought into contact with the catalyst layer is not particularly limited, and specific examples include water vapor, carbon dioxide gas, nitrous oxide, air, oxygen, ozone and the like. Among these, water vapor and carbon dioxide can be used particularly preferably.
本実施の形態に係る金属含有ゼオライト触媒の基体となる中間細孔ゼオライト(Z1)は、四面体型TO4(TはSi原子またはAl原子を示し、Oは酸素原子を示す)ユニット10個からなる10員環構造を有するゼオライトである。当該ゼオライトの、細孔径が0.50~0.65nmの範囲にある細孔が、ゼオライト結晶構造に由来する全細孔の10%以上の容積を占めることが好ましく、20%以上の容積を占めることがより好ましく、50%以上の容積を占めることがさらに好ましい。なお、ゼオライト結晶構造に由来する細孔とは細孔径が0.20~1.0nmの範囲にある細孔を示す。また、ゼオライト結晶構造に由来する細孔の細孔径については、窒素ガス吸着法により測定した吸脱着等温線からt-プロット法を用いて算出する。 [Intermediate pore zeolite (Z1)]
The intermediate pore zeolite (Z1) serving as the base of the metal-containing zeolite catalyst according to the present embodiment is composed of 10 tetrahedral-type TO 4 (T represents Si atom or Al atom, and O represents oxygen atom) unit. It is a zeolite having a 10-membered ring structure. The pores having a pore diameter in the range of 0.50 to 0.65 nm of the zeolite preferably occupy 10% or more of the total pores derived from the zeolite crystal structure, and occupy a volume of 20% or more. More preferably, it occupies a volume of 50% or more. The pore derived from the zeolite crystal structure means a pore having a pore diameter in the range of 0.20 to 1.0 nm. The pore diameter of the pores derived from the zeolite crystal structure is calculated from the adsorption / desorption isotherm measured by the nitrogen gas adsorption method using the t-plot method.
本実施の形態に係る金属含有ゼオライト触媒は、上記中間細孔ゼオライト(Z1)および周期律表8~10族金属(X)を構成要素として含む触媒である。金属含有ゼオライト触媒は、金属(X)を1種類以上含んでいれば効果を発現するが、2種類以上の金属(X)から構成されていてもよい。金属(X)はRu、Rh、Ir、Ni、Pd、およびPtから選ばれることが好ましく、Ru、Rh、Ir、Pd、およびPtから選ばれることがより好ましく、Ru、Rh、Pd、およびPtから選ばれることがさらに好ましい。また、2種類以上の金属(X)から構成されている例としてPtとPdの組み合わせ、PdとRuの組み合わせ、PtとRuの組み合わせなどが挙げられるが、これに限定されるものでは無い。 [Metal-containing zeolite catalyst]
The metal-containing zeolite catalyst according to the present embodiment is a catalyst containing the above-mentioned intermediate pore zeolite (Z1) and periodic table group 8-10 metal (X) as constituent elements. The metal-containing zeolite catalyst exhibits an effect as long as it contains one or more types of metal (X), but may be composed of two or more types of metal (X). The metal (X) is preferably selected from Ru, Rh, Ir, Ni, Pd and Pt, more preferably selected from Ru, Rh, Ir, Pd and Pt, and Ru, Rh, Pd and Pt. More preferably, it is chosen from. Further, examples of two or more types of metal (X) include a combination of Pt and Pd, a combination of Pd and Ru, a combination of Pt and Ru, and the like, but are not limited thereto.
本発明に係わる金属含有ゼオライト触媒は、前記した性状を満たす限り、その触媒の調製方法については特に制限は無い。本発明に係わる触媒の調製方法は、次の方法(1)、(2)および(3)に大別される。
(1)中間細孔ゼオライト(Z1’)に金属(X)と、必要に応じて、元素(Y1)および元素(Y2)から選ばれる1種以上を担持する方法。
(2)中間細孔ゼオライト(Z1’)並びに、金属(X)が担持された前記元素(Y1)の酸化物(Z2)または金属(X)が担持された、前記ゼオライト(Z1’)および前記酸化物(Z2)のいずれとも異なる無機固体化合物(Z3)とを物理混合する方法。
(3)元素(Y2)が担持された中間細孔ゼオライト(Z1’)と、金属(X)が担持された元素(Y1)の酸化物(Z2)または金属(X)が担持された、前記ゼオライト(Z1’)および前記酸化物(Z2)のいずれとも異なる無機固体化合物(Z3)とを物理混合する方法。
なお、方法(2)および方法(3)において、金属(X)の一部が中間細孔ゼオライト(Z1’)に担持されていてもよいものとする。以下の説明では、(Z1’)、(Z2)または(Z3)を「担体」と呼ぶ場合がある。また、方法(1)によって得られる触媒を単一担体型触媒、方法(2)または方法(3)で得られる触媒を複数担体型触媒と呼ぶ場合がある。 [Method for preparing metal-containing zeolite catalyst]
As long as the metal-containing zeolite catalyst according to the present invention satisfies the above-described properties, there is no particular limitation on the method for preparing the catalyst. The method for preparing the catalyst according to the present invention is roughly divided into the following methods (1), (2) and (3).
(1) A method of supporting the metal (X) and, if necessary, one or more selected from the element (Y1) and the element (Y2) on the intermediate pore zeolite (Z1 ′).
(2) The intermediate pore zeolite (Z1 ′), the zeolite (Z1 ′) on which the oxide (Z2) or the metal (X) of the element (Y1) on which the metal (X) is supported, and the metal (X) are supported. A method of physically mixing an inorganic solid compound (Z3) different from any of the oxides (Z2).
(3) The intermediate pore zeolite (Z1 ′) on which the element (Y2) is supported and the oxide (Z2) or metal (X) of the element (Y1) on which the metal (X) is supported, A method of physically mixing zeolite (Z1 ′) and an inorganic solid compound (Z3) different from any of the oxides (Z2).
In the methods (2) and (3), a part of the metal (X) may be supported on the intermediate pore zeolite (Z1 ′). In the following description, (Z1 ′), (Z2) or (Z3) may be referred to as “carrier”. Further, the catalyst obtained by the method (1) may be called a single carrier type catalyst, and the catalyst obtained by the method (2) or the method (3) may be called a multiple carrier type catalyst.
金属(X)、元素(Y)およびその他の元素を担体に担持する場合について、中間細孔ゼオライト(Z1)、元素(Y1)の酸化物(Z2)、前記ゼオライト(Z1)および前記酸化物(Z2)のいずれとも異なる無機固体化合物(Z3)およびこれらの混合物が担体となる。担持する手法としては、公知の手法が特に制限無く用いられる。例えば、金属(X)、元素(Y)およびその他の元素を、単体または化合物の形態で所望の量含む溶液を作製し、中間細孔ゼオライト(Z1)、元素(Y1)の酸化物(Z2)または無機固体化合物(Z3)と接触させる含浸法、金属(X)、元素(Y)およびその他の元素を単体または化合物の形態で気化させ気体として中間細孔ゼオライト(Z1)、元素(Y1)の酸化物(Z2)または無機固体化合物(Z3)と接触させる蒸着法等が知られる。より具体的には、含浸法としてはポアフィリング法、インシピエント・ウェットネス(incipient wetness)法、平衡吸着法、蒸発乾固法、噴霧乾燥法、沈着法、およびイオン交換法等、蒸着法としては化学蒸着法、物理蒸着法等が挙げられる。好ましい手法としては操作が比較的簡便で特殊な装置が不要な含浸法が挙げられる。 (Support)
In the case of supporting the metal (X), the element (Y) and other elements on the support, the intermediate pore zeolite (Z1), the oxide (Z2) of the element (Y1), the zeolite (Z1) and the oxide ( An inorganic solid compound (Z3) different from any of Z2) and a mixture thereof serve as a carrier. As a method for supporting, a known method is used without any particular limitation. For example, a solution containing a desired amount of metal (X), element (Y) and other elements in the form of a simple substance or a compound is prepared, and intermediate pore zeolite (Z1), oxide of element (Y1) (Z2) Alternatively, the impregnation method in contact with the inorganic solid compound (Z3), the metal (X), the element (Y) and other elements are vaporized in the form of a simple substance or a compound to form a gas of the intermediate pore zeolite (Z1) or the element (Y1). A vapor deposition method for contacting with an oxide (Z2) or an inorganic solid compound (Z3) is known. More specifically, the impregnation method includes pore filling method, incipient wetness method, equilibrium adsorption method, evaporation to dryness method, spray drying method, deposition method, and ion exchange method. Examples include chemical vapor deposition and physical vapor deposition. A preferred method is an impregnation method that is relatively easy to operate and does not require special equipment.
前記触媒調製方法(2)および(3)において実施される物理混合によって複数担体型触媒を調製する際の、物理混合の方法については特に制限は無いが、好ましい方法として具体的には、(a)混合の対象となる固体成分を全て粉体同士で混合する方法、(b)混合の対象となる固体成分を同じ溶媒中に分散させてスラリー状とした後に蒸発乾固する方法、(c)混合の対象となる固体成分を成形体として成形体同士を混合する方法、(d)混合の対象となる各要素をそれぞれ個別の層として共存させる方法、(e)前記(a)~(c)の方法を併用した混合、が挙げられる。(b)について、混合の対象となる固体成分を複数含んだ成形体を調製し、他の成形体と混合してもよい。(d)の例として、固定床の反応器に各成分を順番に堆積させ複数の層から成る触媒層を形成させる方法が挙げられる。中でも(a)、(b)、(c)および(e)の方法がより好ましく、(a)および(b)の方法が最も好ましい。 [Physical mixing]
There is no particular limitation on the method of physical mixing when preparing a multi-support catalyst by physical mixing carried out in the catalyst preparation methods (2) and (3), but specific examples of preferred methods include (a ) A method in which all solid components to be mixed are mixed with each other in powder form, (b) a method in which the solid components to be mixed are dispersed in the same solvent to form a slurry, and then evaporated to dryness, (c) (D) a method in which each component to be mixed coexists as an individual layer, (e) the above-mentioned (a) to (c) And a combination of the above methods. About (b), you may prepare the molded object containing multiple solid components used as the object of mixing, and may mix with another molded object. As an example of (d), there is a method in which each component is sequentially deposited in a fixed bed reactor to form a catalyst layer composed of a plurality of layers. Among these, the methods (a), (b), (c) and (e) are more preferable, and the methods (a) and (b) are most preferable.
(触媒前処理)
反応に使用する金属含有ゼオライト触媒は、必要に応じて反応前に前処理を施してもよい。前処理として具体的には、(1)触媒表面の吸着物質除去を目的とした、窒素およびヘリウム等の不活性な気体を流通しながらの高温処理、(2)触媒の金属成分還元を目的とした、水素または希釈水素を流通しながらの高温還元処理、等が挙げられる。前処理の種類、回数、順序について特に制限は無いが、上述の(2)を含む前処理を施すことが好ましい。 [Catalytic decomposition reaction]
(Catalyst pretreatment)
The metal-containing zeolite catalyst used for the reaction may be pretreated before the reaction, if necessary. Specifically, the pretreatment is as follows: (1) high temperature treatment with inert gas such as nitrogen and helium for the purpose of removing the adsorbed material on the catalyst surface, and (2) reduction of metal components of the catalyst. And high-temperature reduction treatment while circulating hydrogen or diluted hydrogen. Although there is no restriction | limiting in particular about the kind, frequency | count, and order of pre-processing, It is preferable to perform the pre-processing including said (2).
原料および酸化性ガスの触媒層への供給方法については特に制限は無いが、原料および酸化性ガスを触媒層全体に均一に接触させるため、いずれについても常温で液体のものについては加熱等により予め気化させ、全て気体として触媒層に供給することが好ましい。また原料と酸化性ガスの混合状態についても特に制限は無いが、両者を混合した後に触媒層に供給することが好ましい。なお、酸化性ガスは触媒層における反応の結果生成させることにより触媒層と接触させることも可能であるが、少なくとも酸化ガスの一部は原料と混合した後に触媒層に供給することが望ましい。また、原料ガスおよび酸化性ガスは各々を連続的に供給しても不連続的に供給してもよい。例えば、原料ガスの供給を一時的に停止して酸化性ガスのみを触媒層に供給し、再び原料ガスを触媒層に供給する方法であってもよい。不連続的にガスを供給する方法としては、以下に説明する第1の方法と第2の方法とを挙げることができる。第1の方法は、原料ガスと酸化性ガスの両方が触媒層に供給されている状態で、原料ガスの供給を一時的に停止して酸化性ガスを触媒層に供給し、その後、再び原料ガスを触媒層に供給する方法である。第2の方法は、触媒層に原料ガスのみが供給されている状態で、原料ガスの供給を一時的に停止して酸化性ガスを供給し、その後、再び原料ガスを触媒層に供給する方法である。第2の方法において再び原料ガスを触媒層に供給する際には、原料ガスを酸化性ガスとともに供給してもよいし、原料ガスのみを供給してもよい。 (Raw material and oxidizing gas supply)
There are no particular restrictions on the method of supplying the raw material and the oxidizing gas to the catalyst layer. However, in order to uniformly bring the raw material and the oxidizing gas into contact with the entire catalyst layer, both of them are liquid at normal temperature by heating or the like in advance. It is preferable to vaporize and supply all as gas to the catalyst layer. Moreover, there is no restriction | limiting in particular about the mixed state of a raw material and oxidizing gas, However, After mixing both, supplying to a catalyst layer is preferable. The oxidizing gas can be brought into contact with the catalyst layer by being generated as a result of the reaction in the catalyst layer, but it is desirable to supply at least a part of the oxidizing gas to the catalyst layer after mixing with the raw material. The source gas and the oxidizing gas may be supplied continuously or discontinuously. For example, a method may be used in which the supply of the source gas is temporarily stopped, only the oxidizing gas is supplied to the catalyst layer, and the source gas is supplied again to the catalyst layer. Examples of the method for supplying gas discontinuously include a first method and a second method described below. In the first method, in a state where both the raw material gas and the oxidizing gas are supplied to the catalyst layer, the supply of the raw material gas is temporarily stopped to supply the oxidizing gas to the catalyst layer, and then the raw material is again supplied. In this method, gas is supplied to the catalyst layer. The second method is a method in which only the source gas is supplied to the catalyst layer, the supply of the source gas is temporarily stopped to supply the oxidizing gas, and then the source gas is supplied again to the catalyst layer. It is. When the source gas is supplied again to the catalyst layer in the second method, the source gas may be supplied together with the oxidizing gas or only the source gas may be supplied.
接触分解反応は一般に吸熱反応であるため、反応温度が高いほど反応の進行は熱力学的に有利となるが、ナフサ熱分解で汎用される800℃以上の高温はゼオライト触媒には過酷な条件であり、短時間で活性が低下してしまう。一方で、不飽和炭化水素類の生成を妨げず、かつ酸化性ガスによるコークおよびコーク前駆体の除去が進行する程度の高温で反応行う必要がある。これらの制約から、接触分解反応における触媒層の温度は、好ましくは500~750℃の範囲、より好ましくは600~700℃の範囲である。なお、本発明のナフサ等低級飽和炭化水素類の接触分解反応における反応温度とは触媒層の温度であり、触媒層の温度は触媒層全体の平均的な温度を意味する。しかしながら、外部から加熱されているため局所的に温度が高い反応器壁付近や、分解反応による吸熱の影響を大きく受けて特に温度が低い箇所等では、触媒層全体の平均的な温度から大きく外れる場合がある。そのため、触媒層全体の平均的な温度を測定するためには、特殊な環境でない箇所を選んで測定する必要がある。具体的な測定方法として、例えば、固定床式反応器の場合であれば、触媒層の反応管軸方向の両端および中央の温度を反応管断面の中心付近において測定し、3点の温度の平均を取る方法等が挙げられる。 (Reaction temperature)
Since the catalytic cracking reaction is generally endothermic, the higher the reaction temperature, the more thermodynamically advantageous the reaction proceeds. However, the high temperatures of 800 ° C. and higher, which are commonly used in naphtha pyrolysis, are severe conditions for zeolite catalysts. Yes, the activity decreases in a short time. On the other hand, it is necessary to carry out the reaction at a high temperature that does not interfere with the production of unsaturated hydrocarbons and that allows removal of coke and coke precursors with an oxidizing gas. From these restrictions, the temperature of the catalyst layer in the catalytic cracking reaction is preferably in the range of 500 to 750 ° C., more preferably in the range of 600 to 700 ° C. The reaction temperature in the catalytic cracking reaction of lower saturated hydrocarbons such as naphtha of the present invention is the temperature of the catalyst layer, and the temperature of the catalyst layer means the average temperature of the entire catalyst layer. However, since it is heated from the outside, it is greatly deviated from the average temperature of the entire catalyst layer in the vicinity of the reactor wall where the temperature is locally high, or the location where the temperature is particularly low due to the influence of the endotherm due to the decomposition reaction. There is a case. Therefore, in order to measure the average temperature of the entire catalyst layer, it is necessary to select and measure a location that is not a special environment. As a specific measurement method, for example, in the case of a fixed bed reactor, the temperatures of both ends and the center of the catalyst layer in the axial direction of the catalyst layer are measured in the vicinity of the center of the cross section of the reaction tube, and the average of three temperatures The method of taking.
本発明の製造方法において、飽和炭化水素類の不飽和炭化水素類への転化は分解反応であるため、原料の分圧が高くなるほど反応の進行は熱力学的に不利になるといえる。一方で原料の分圧が低すぎるのは経済性の観点から好ましくない。そのため、原料の分圧(原料が混合物である場合は全反応生成物の分圧の合計)は0.01~0.20MPaの範囲内であることが好ましい。反応器内の全圧については特に制限は無いが0.1~1.0MPaの範囲内であることが好ましい。 (Reaction pressure)
In the production method of the present invention, since the conversion of saturated hydrocarbons to unsaturated hydrocarbons is a decomposition reaction, it can be said that the progress of the reaction becomes thermodynamically disadvantageous as the partial pressure of the raw material increases. On the other hand, it is not preferable from the viewpoint of economy that the partial pressure of the raw material is too low. For this reason, the partial pressure of the raw material (when the raw material is a mixture, the total partial pressure of all reaction products) is preferably in the range of 0.01 to 0.20 MPa. The total pressure in the reactor is not particularly limited but is preferably in the range of 0.1 to 1.0 MPa.
原料および酸化性ガスの供給量について特に制限は無いが、酸化性ガスにより一定以上のコーク生成抑制効果を得ると同時に、酸化性ガスによる触媒の劣化や過剰な反応の進行による影響を最小限とするために、原料の供給量に対する酸化性ガスの供給量の比を一定の範囲内に抑えることが望ましい。具体的な実施形態としては、反応温度において原料(O)の気体が占める体積(VO)に対する、反応温度において前記酸化性ガス(S)の気体が占める体積(VS)の比(VS/VO)は、0.01~2の範囲にあることが好ましく、0.01~1の範囲にあることがより好ましく、0.1~1の範囲にあることが最も好ましい。なお、ナフサ等混合物が原料の場合には分子量が明確でないため、平均分子量をn-ヘキサンの分子量と同じ86と仮定してVOを算出し、VOおよびVSはいずれも触媒層と接触する前の気体の体積として計算するものとする。 (Raw material and oxidizing gas supply)
There are no particular restrictions on the amount of raw materials and oxidizing gas supplied, but at least a certain level of coke formation suppression effect can be obtained with oxidizing gas, while at the same time minimizing the effects of catalyst deterioration and excessive reaction progress due to oxidizing gas. Therefore, it is desirable to keep the ratio of the supply amount of the oxidizing gas to the supply amount of the raw material within a certain range. As a specific embodiment, the ratio (V S ) of the volume (V S ) occupied by the gas of the oxidizing gas (S) at the reaction temperature to the volume (V O ) occupied by the gas of the raw material (O) at the reaction temperature. / V O ) is preferably in the range of 0.01 to 2, more preferably in the range of 0.01 to 1, and most preferably in the range of 0.1 to 1. In addition, since the molecular weight is not clear when a mixture such as naphtha is a raw material, V O is calculated assuming that the average molecular weight is 86, which is the same as the molecular weight of n-hexane, and both V O and V S are in contact with the catalyst layer. It shall be calculated as the volume of the gas before
原料と触媒との接触時間について特に制限は無いが、反応が十分に進行し、かつ、反応進行の妨げになるほどのコーキングをもたらさない程度の接触時間が好ましい。具体的には、下記式(1)で定義される中間細孔ゼオライト(Z1)成分質量当たりの重量空間速度(WHSV)が0.1~30h-1の範囲で行うことが好ましく、0.1~15h-1の範囲で行うことがより好ましい。
(WHSV[h-1])=(原料供給量[g/h])/(中間細孔ゼオライト(Z1)成分の質量[g])・・・(1) (Contact time)
Although there is no restriction | limiting in particular about the contact time of a raw material and a catalyst, The contact time of the grade which does not produce coking so that reaction fully advances and reaction progress is not preferable. Specifically, it is preferable that the weight hourly space velocity (WHSV) per mass of the intermediate pore zeolite (Z1) component defined by the following formula (1) is in the range of 0.1 to 30 h −1 , More preferably, it is carried out in the range of ˜15 h −1 .
(WHSV [h −1 ]) = (raw material supply amount [g / h]) / (mass of intermediate pore zeolite (Z1) component [g]) (1)
酸化セリウム(IV)(Strem Chemicals社製)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、1.0gのヘキサアンミンルテニウム(III)(Sigma-Aldrich社製)を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、酸化セリウム(IV)1.0g当たり330μmolのRuを含有するRu/CeO2を調製した。 [Catalyst Preparation Example 1] Preparation of metal-containing zeolite catalyst (Ru / CeO 2 + P / ZSM5) 10 g of cerium (IV) oxide (manufactured by Strem Chemicals) was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. A solution prepared by dissolving 1.0 g of hexaammineruthenium (III) (manufactured by Sigma-Aldrich) in 100 ml of distilled water was gradually added to the cerium (IV) oxide / water mixture at room temperature. The mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Ru / CeO 2 containing 330 μmol of Ru per 1.0 g of cerium (IV) oxide.
酸化セリウム(IV)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、0.87gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、酸化セリウム(IV)1.0g当たり330μmolのPdを含有するPd/CeO2を調製した。 [Catalyst Preparation Example 2] Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + P / ZSM5) 10 g of cerium (IV) oxide was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. A solution prepared by dissolving 0.87 g of tetraamminepalladium (II) chloride monohydrate in 100 ml of distilled water was gradually added to the cerium (IV) oxide / water mixture at room temperature, and 2% at 50 ° C. After stirring for an hour, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd / CeO 2 containing 330 μmol of Pd per 1.0 g of cerium (IV) oxide.
酸化セリウム(IV)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、0.96gの硝酸ニッケル(II)塩化物六水和物(和光純薬工業社製)を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、酸化セリウム(IV)1.0g当たり330μmolのNiを含有するNi/CeO2を調製した。 [Catalyst Preparation Example 3] Preparation of metal-containing zeolite catalyst (Ni / CeO 2 + P / ZSM5) 10 g of cerium (IV) oxide was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. A solution obtained by dissolving 0.96 g of nickel nitrate (II) chloride hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 100 ml of distilled water is gradually added to the cerium (IV) oxide / water mixture at room temperature. The mixture was stirred at 50 ° C. for 2 hours, and further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Ni / CeO 2 containing 330 μmol of Ni per 1.0 g of cerium (IV) oxide.
Aluminum Cerium Oxide(CeAlO3、Sigma-Aldrich社製)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。このCeAlO3(IV)/水の混合液に対し、0.87gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、CeAlO3(IV)1.0g当たり330μmolのPdを含有するPd/CeAlO3を調製した。 [Catalyst Preparation Example 4] Preparation of metal-containing zeolite catalyst (Pd / CeAlO 3 + P / ZSM5) 10 g of aluminum cerium oxide (CeAlO 3 , manufactured by Sigma-Aldrich) was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. . To this CeAlO 3 (IV) / water mixture, a solution of 0.87 g of tetraamminepalladium (II) chloride monohydrate dissolved in 100 ml of distilled water was gradually added at room temperature, After stirring for an hour, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd / CeAlO 3 containing 330 μmol of Pd per 1.0 g of CeAlO 3 (IV).
25質量%アンモニア水(和光純薬工業社製)460mlと蒸留水140mlを混合して19質量%アンモニア水600mlを調製した。調製したアンモニア水を攪拌しながら、8.7gの硝酸ランタン六水和物(和光純薬工業社製)および5.7gの硝酸マンガン六水和物(関東化学社製)を200mlの蒸留水に溶解した溶液を室温において1時間かけて滴下し、さらに攪拌しながら室温にて1時間、その後攪拌せずに室温にて0.5時間静置し熟成させた。得られた混合物を濾過し、濾物を乾燥した後に乳鉢にて粉砕し、空気中750℃で5時間焼成してLaMnO3を調製した。 [Catalyst Preparation Example 5] Preparation of metal-containing zeolite catalyst (Pd / LaMnO 3 + P / ZSM5) 460 ml of 25% by mass ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) and 140 ml of distilled water were mixed to obtain 600 ml of 19% by mass ammonia water. Prepared. While stirring the prepared aqueous ammonia, 8.7 g of lanthanum nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 5.7 g of manganese nitrate hexahydrate (manufactured by Kanto Chemical Co., Ltd.) were added to 200 ml of distilled water. The dissolved solution was added dropwise at room temperature over 1 hour, and further aged at room temperature for 1 hour with stirring, and then allowed to stand at room temperature for 0.5 hour without stirring. The obtained mixture was filtered, and the filtrate was dried and then pulverized in a mortar, and calcined in the air at 750 ° C. for 5 hours to prepare LaMnO 3 .
n-ペンタン29質量%、n-へキサン14質量%、2-メチルペンタン14質量%、n-オクタン29質量%、メチルシクロヘキサン7質量%、シクロヘキサン7質量%となるよう試薬を混合し、十分に攪拌した液を合成ナフサとした。 [Example 1] Activity evaluation: synthetic naphtha decomposition reaction n-pentane 29% by mass, n-hexane 14% by mass, 2-methylpentane 14% by mass, n-octane 29% by mass, methylcyclohexane 7% by mass, cyclohexane 7 The reagent was mixed so that it might become the mass%, and the liquid fully stirred was used as the synthetic naphtha.
触媒調製例2で調製したPd/CeO2+P/ZSM5触媒について、触媒としてPd/CeO2+P/ZSM5を0.86g充填した以外は実施例1と同様にして、合成ナフサ分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表1に示す。 [Example 2]
The activity of the Pd / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 2 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Pd / CeO 2 + P / ZSM5 was charged as a catalyst. . Table 1 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例2で調製したPd/CeO2+P/ZSM5触媒について、水蒸気供給量を3.8g/h、全圧を0.35MPaとした以外は実施例1と同様にして、中間細孔ゼオライト質量当たりのWHSVが10h-1、VS/VOが2.4の条件で合成ナフサ分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表1に示す。 [Example 3]
For the Pd / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 2, the mass of intermediate pore zeolite was the same as in Example 1 except that the water vapor supply rate was 3.8 g / h and the total pressure was 0.35 MPa. The activity was evaluated by a synthetic naphtha decomposition reaction under the conditions of a per unit WHSV of 10 h −1 and a V S / V O of 2.4. Table 1 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例3で調製したNi/CeO2+P/ZSM5触媒について、触媒としてNi/CeO2+P/ZSM5を0.86g充填した以外は実施例1と同様にして、合成ナフサ分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表1に示す。 [Example 4]
The activity of the Ni / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 3 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Ni / CeO 2 + P / ZSM5 was charged as a catalyst. . Table 1 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例4で調製したPd/CeAlO3+P/ZSM5触媒について、触媒としてPd/CeAlO3+P/ZSM5を0.86g充填した以外は実施例1と同様にして、合成ナフサ分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表1に示す。 [Example 5]
The activity of the Pd / CeAlO 3 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 4 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Pd / CeAlO 3 + P / ZSM5 was charged as a catalyst. . Table 1 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例5で調製したPd/LaMnO3+P/ZSM5触媒について、触媒としてPd/LaMnO3+P/ZSM5を0.86g充填した以外は実施例1と同様にして、合成ナフサ分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表1に示す。 [Example 6]
The activity of the Pd / LaMnO 3 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 5 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Example 1 except that 0.86 g of Pd / LaMnO 3 + P / ZSM5 was charged as a catalyst. . Table 1 shows the yield of each product calculated based on the mass of the carbon component.
中間細孔ゼオライトであるSiO2/Al2O3モル比500のNH4 +型のMFIゼオライト(Sued-Chemie Catalysts社製)を空気中500℃で4時間焼成することにより、SiO2/Al2O3モル比500のH+型のMFIゼオライト触媒(H-ZSM5)を調製した。 [Comparative Example 1]
An intermediate pore zeolite SiO 2 / Al 2 O 3 molar ratio of NH 4 + type MFI zeolite (manufactured by Sued-Chemie Catalysts) is calcined in air at 500 ° C. for 4 hours to obtain SiO 2 / Al 2. An H + type MFI zeolite catalyst (H-ZSM5) with an O 3 molar ratio of 500 was prepared.
触媒調製例1で調製したP/ZSM5触媒について、触媒としてP/ZSM5を0.79g充填した以外は比較例1と同様にして、合成ナフサ分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表1に示す。 [Comparative Example 2]
The activity of the P / ZSM5 catalyst prepared in Catalyst Preparation Example 1 was evaluated by a synthetic naphtha decomposition reaction in the same manner as in Comparative Example 1 except that 0.79 g of P / ZSM5 was charged as a catalyst. Table 1 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例1で調製したRu/CeO2+P/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてRu/CeO2+P/ZSM5を0.86g充填し、大気圧下、窒素を50Ncc/minの流量で反応器内に流通させながら600℃まで昇温した。600℃において、水素を50Ncc/minの流量で反応器内に流通させながら1時間還元処理を行った。還元処理後、600℃において、流通ガスを水素から窒素に切り替え、50Ncc/minの流量で反応器内に流通させながら1.5時間前処理し、反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料の合成ナフサを7.5g/h流量で全圧が0.10MPaとなるように加圧して反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが10h-1、反応温度における原料である合成ナフサ気体と酸化性ガスである水蒸気の体積比VS/VOが0、合成ナフサ気体の分圧が0.11MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表1に示す。 [Comparative Example 3]
The Ru / CeO 2 + P / ZSM5 catalyst prepared in Catalyst Preparation Example 1 was pressed and compressed to form agglomerates. The agglomerates were crushed and sized to a particle size of 0.25 mm to 0.50 mm and fixed. The activity was evaluated by n-hexane decomposition reaction using a bed flow type reactor. The reaction tube was filled with 0.86 g of Ru / CeO 2 + P / ZSM5 as a catalyst, and the temperature was raised to 600 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 600 ° C., reduction treatment was performed for 1 hour while flowing hydrogen through the reactor at a flow rate of 50 Ncc / min. After the reduction treatment, at 600 ° C., the flow gas was switched from hydrogen to nitrogen, pretreatment was performed for 1.5 hours while flowing in the reactor at a flow rate of 50 Ncc / min, and the temperature was raised to 650 ° C. of the reaction temperature. At 650 ° C., the nitrogen circulated in the reaction tube was stopped, and instead, the raw material synthetic naphtha was pressurized to a total pressure of 0.10 MPa at a flow rate of 7.5 g / h and supplied to the reaction tube. WHSV per pore zeolite mass is 10 h −1 , volume ratio V S / V O of synthetic naphtha gas as raw material and water vapor as oxidizing gas at reaction temperature is 0, and partial pressure of synthetic naphtha gas is 0.11 MPa The reaction was started. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 1 shows the yield of each product calculated based on the mass of the carbon component.
100mlの蒸留水にベーマイト(和光純薬工業社製)0.67gおよびリン酸水素二アンモニウム(和光純薬工業社製)1.7gを添加して室温で攪拌した混合液に、触媒調製例1で調製したSiO2/Al2O3モル比30のH-ZSM5(10g)を添加しさらに室温で攪拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中600℃で5時間焼成し、さらに窒素160Ncc/minおよび水蒸気40Ncc/minの流量となるよう窒素と水蒸気の混合ガスを流通させながら700℃で24時間水蒸気処理してAl-P/ZSM5を調製した。 [Catalyst Preparation Example 6] Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + Al-P / ZSM5) Boehmite (manufactured by Wako Pure Chemical Industries, Ltd.) 0.67 g and diammonium hydrogen phosphate (Wako Pure Chemical Industries, Ltd.) in 100 ml of distilled water H-ZSM5 (10 g) having a SiO 2 / Al 2 O 3 molar ratio of 30 prepared in Catalyst Preparation Example 1 was added to the mixed solution obtained by adding 1.7 g and stirring at room temperature, and stirring at room temperature. did. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness is dried and then calcined in air at 600 ° C. for 5 hours, and further at a temperature of 700 ° C. for 24 hours while flowing a mixed gas of nitrogen and water vapor so that the flow rate is 160 Ncc / min of nitrogen and 40 Ncc / min of water vapor. Al—P / ZSM5 was prepared by steam treatment.
Pd/CeO20.23gの代わりに、触媒調製例1で調製したRu/CeO20.23gを用いた以外は触媒調製例6と同様にして、Ru/CeO2+Al-P/ZSM5を調製した。 [Catalyst Preparation Example 7] Preparation of metal-containing zeolite catalyst (Ru / CeO 2 + Al-P / ZSM5) Instead of 0.23 g of Pd / CeO 2, 0.23 g of Ru / CeO 2 prepared in Catalyst Preparation Example 1 was used. Ru / CeO 2 + Al—P / ZSM5 was prepared in the same manner as in Catalyst Preparation Example 6 except that
酸化セリウム(IV)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、0.44gのテトラアンミンパラジウム(II)塩化物一水和物および0.85gの塩化白金(IV)酸六水和物(和光純薬工業社製)を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し1.0g当たり165μmolのPdおよび165μmolのPtを含有するPd-Pt/CeO2を調製した。 [Catalyst Preparation Example 8] Preparation of metal-containing zeolite catalyst (Pd—Pt / CeO 2 + Al—P / ZSM5) 10 g of cerium (IV) oxide was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. For this cerium (IV) oxide / water mixture, 0.44 g of tetraamminepalladium (II) chloride monohydrate and 0.85 g of platinum chloride (IV) acid hexahydrate (Wako Pure Chemical Industries, Ltd.) Was dissolved in 100 ml of distilled water at room temperature, stirred at 50 ° C. for 2 hours, and further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd—Pt / CeO 2 containing 165 μmol Pd and 165 μmol Pt per 1.0 g.
触媒調製例6で調製したPd/CeO2+Al-P/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてPd/CeO2+Al-P/ZSM5(0.94g)を充填し、大気圧下、窒素を50Ncc/minの流量で反応器内に流通させながら400℃まで昇温した。400℃において、水素を50Ncc/minの流量で反応器内に流通させながら1時間還元処理を行った。還元処理後、400℃において、流通ガスを水素から窒素に切り替え、50Ncc/minの流量で反応器内に流通させながら1.5時間前処理し、反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび水蒸気を0.75g/hの流量で全圧が0.10MPaとなるよう反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが10h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである水蒸気の体積比VS/VOが0.48、n-へキサン気体の分圧が0.068MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表2に示す。 [Example 7] Activity evaluation: n-hexane decomposition reaction The Pd / CeO 2 + Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 6 was pressed and compressed into aggregates, and the aggregates were crushed. The particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was filled with Pd / CeO 2 + Al—P / ZSM5 (0.94 g) as a catalyst, and the temperature was raised to 400 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 400 ° C., reduction treatment was performed for 1 hour while flowing hydrogen through the reactor at a flow rate of 50 Ncc / min. After the reduction treatment, at 400 ° C., the flow gas was switched from hydrogen to nitrogen, pre-treated for 1.5 hours while flowing in the reactor at a flow rate of 50 Ncc / min, and the temperature was raised to the reaction temperature of 650 ° C. At 650 ° C., the nitrogen flowing through the reaction tube was stopped, and instead, the reaction was carried out so that the total pressure became 0.10 MPa at a flow rate of 7.5 g / h for raw material n-hexane and 0.75 g / h for water vapor. WHSV per mass of intermediate pore zeolite is 10 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 0.48, n The reaction was started under the condition that the partial pressure of hexane gas was 0.068 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 2 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例7で調製したRu/CeO2+Al-P/ZSM5触媒について、触媒としてRu/CeO2+Al-P/ZSM5を0.94g充填した以外は実施例7と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表2に示す。 [Example 8]
In the same manner as in Example 7, except that the Ru / CeO 2 + Al—P / ZSM5 catalyst prepared in Catalyst Preparation Example 7 was charged with 0.94 g of Ru / CeO 2 + Al—P / ZSM5 as a catalyst, n-hexane The activity was evaluated by a decomposition reaction. Table 2 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例8で調製したPd-Pt/CeO2+Al-P/ZSM5触媒について、触媒としてPd-Pt/CeO2+Al-P/ZSM5を0.94g充填した以外は実施例7と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表2に示す。 [Example 9]
The Pd—Pt / CeO 2 + Al—P / ZSM5 catalyst prepared in Catalyst Preparation Example 8 was the same as in Example 7 except that 0.94 g of Pd—Pt / CeO 2 + Al—P / ZSM5 was charged as a catalyst. The activity was evaluated by n-hexane decomposition reaction. Table 2 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例6で調製したAl-P/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてAl-P/ZSM5を0.87g充填し、大気圧下、窒素を50Ncc/minの流量で反応器内に流通させながら反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび水蒸気を0.75g/hの流量で全圧が0.10MPaとなるよう反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが10h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである水蒸気の体積比VS/VOが0.48、n-へキサン気体の分圧が0.068MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表2に示す。 [Comparative Example 4]
The Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 6 was pressed and compressed to form agglomerates. The agglomerates were crushed and sized to a particle size of 0.25 mm to 0.50 mm, and then passed through a fixed bed. The activity was evaluated by n-hexane decomposition reaction using a reaction apparatus. The reaction tube was charged with 0.87 g of Al—P / ZSM5 as a catalyst, and the temperature was raised to 650 ° C. of the reaction temperature while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 650 ° C., the nitrogen flowing through the reaction tube was stopped, and instead, the reaction was carried out so that the total pressure became 0.10 MPa at a flow rate of 7.5 g / h for raw material n-hexane and 0.75 g / h for water vapor. WHSV per mass of intermediate pore zeolite is 10 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 0.48, n The reaction was started under the condition that the partial pressure of hexane gas was 0.068 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 2 shows the yield of each product calculated based on the mass of the carbon component.
酸化セリウム(IV)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、0.87gのテトラアンミンパラジウム(II)塩化物一水和物および1.0gのヘキサアンミンルテニウム(III)を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、酸化セリウム(IV)1.0g当たり330μmolのPdおよび330μmolのRuを含有するPd-Ru/CeO2を調製した。 [Catalyst Preparation Example 9] Preparation of metal-containing zeolite catalyst (Pd—Ru / CeO 2 + Al—P / ZSM5) 10 g of cerium (IV) oxide was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. A solution prepared by dissolving 0.87 g of tetraamminepalladium (II) chloride monohydrate and 1.0 g of hexaammineruthenium (III) in 100 ml of distilled water was added to the cerium (IV) oxide / water mixture. The mixture was gradually added at room temperature, stirred at 50 ° C. for 2 hours, and further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd—Ru / CeO 2 containing 330 μmol of Pd and 330 μmol of Ru per 1.0 g of cerium (IV) oxide.
触媒調製例9で調製したPd-Ru/CeO2+Al-P/ZSM5触媒について、触媒としてPd-Ru/CeO2+Al-P/ZSM5を0.94g充填した以外は実施例7と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表3に示す。 [Example 10] Activity evaluation: n-hexane decomposition reaction For the Pd-Ru / CeO 2 + Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 9, 0 was used as the catalyst for Pd-Ru / CeO 2 + Al-P / ZSM5. The activity was evaluated by n-hexane decomposition reaction in the same manner as in Example 7 except that .94 g was charged. Table 3 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例6で調製したAl-P/ZSM5と触媒調製例9で調製したPd-Ru/CeO2をそれぞれ別々に加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒した。整粒したAl-P/ZSM5(0.87g)を反応管に最初に充填し、その後から整粒したPd-Ru/CeO20.075gを充填することで、Pd-Ru/CeO2層およびAl-P/ZSM5触媒層をそれぞれ個別の層として共存させ、原料がPd-Ru/CeO2層、Al-P/ZSM5層の順に接触するように配置させた。このように触媒を充填した反応器を用いて、実施例7と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表3に示す。 [Example 11]
Al-P / ZSM5 prepared in Catalyst Preparation Example 6 and Pd-Ru / CeO 2 prepared in Catalyst Preparation Example 9 were separately pressed and compressed into aggregates, and the aggregates were crushed to 0.25 mm. The particle size was adjusted to a particle size of ˜0.50 mm. The sized Al—P / ZSM5 (0.87 g) is first charged into the reaction tube, and then 0.075 g of sized Pd—Ru / CeO 2 is added to the Pd—Ru / CeO 2 layer and The Al—P / ZSM5 catalyst layers were allowed to coexist as individual layers, and the raw materials were arranged so as to contact the Pd—Ru / CeO 2 layer and the Al—P / ZSM5 layer in this order. Using the reactor packed with the catalyst in this manner, the activity was evaluated by n-hexane decomposition reaction in the same manner as in Example 7. Table 3 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例6で調製したAl-P/ZSM5(2.0g)に対して、Ptの担持量がPt原子として0.50質量%、Ceの担持量がCe原子として0.30質量%となるように、塩化白金(IV)酸六水和物および硝酸セリウム(III)六水和物(和光純薬工業社製)を適量の蒸留水に溶解させた溶液を用いてインシピエント・ウェットネス(incipient wetness)法により担持した。乾燥して得た粉末に対し、ヒドラジン一水和物(和光純薬工業社製)を蒸留水に溶解させて調製した0.13mol/Lのヒドラジン水溶液を滴下してPtを液相還元した後、蒸留水で濾過洗浄し、100℃で24時間乾燥してPt-Ce/Al-P/ZSM5を調製した。 [Catalyst Preparation Example 10] Preparation of Metal-Containing Zeolite Catalyst (Pt—Ce / Al—P / ZSM5) With respect to Al—P / ZSM5 (2.0 g) prepared in Catalyst Preparation Example 6, the supported amount of Pt was Pt. Platinum chloride (IV) acid hexahydrate and cerium (III) nitrate hexahydrate (Wako Pure Chemical Industries, Ltd.) so that 0.50 mass% as atoms and the supported amount of Ce as 0.30 mass% as Ce atoms Kogyo Kogyo Co., Ltd.) was supported by an incipient wetness method using a solution in which an appropriate amount of distilled water was dissolved. After liquid-phase reduction of Pt by adding 0.13 mol / L hydrazine aqueous solution prepared by dissolving hydrazine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in distilled water to the powder obtained by drying. Then, it was filtered and washed with distilled water and dried at 100 ° C. for 24 hours to prepare Pt—Ce / Al—P / ZSM5.
触媒調製例10で調製したPt-Ce/Al-P/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてPt-Ce/Al-P/ZSM5を0.91g充填し、大気圧下、窒素を反応器内に流通させながら反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび水蒸気を2.3g/hの流量で全圧が0.10MPaとなるように反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが10h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである水蒸気の体積比VS/VOが1.4、n-へキサン気体の分圧が0.041MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表4に示す。 [Example 12] Activity evaluation: n-hexane decomposition reaction The Pt-Ce / Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 10 was pressed and compressed into aggregates, and the aggregates were crushed. The particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was filled with 0.91 g of Pt—Ce / Al—P / ZSM5 as a catalyst and heated to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor at atmospheric pressure. At 650 ° C., the nitrogen flowing through the reaction tube was stopped, and instead, the total pressure was 0.10 MPa at a flow rate of raw material n-hexane of 7.5 g / h and water vapor of 2.3 g / h. WHSV per mass of intermediate pore zeolite is 10 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and water vapor as the oxidizing gas is 1.4 at the reaction temperature, The reaction was started under the condition that the partial pressure of n-hexane gas was 0.041 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 4 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例6で調製したAl-P/ZSM5触媒について、触媒としてAl-P/ZSM5を0.87g充填した以外は実施例12と同様にして、n-へキサン分解反応により評価した。炭素成分の質量をベースとして算出した各生成物の収率を表4に示す。 [Comparative Example 5]
The Al—P / ZSM5 catalyst prepared in Catalyst Preparation Example 6 was evaluated by n-hexane decomposition reaction in the same manner as in Example 12 except that 0.87 g of Al—P / ZSM5 was charged as a catalyst. Table 4 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例6で調製したPd/CeO2+Al-P/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてPd/CeO2+Al-P/ZSM5(2.4g)充填し、大気圧下、窒素を50Ncc/minの流量で反応器内に流通させながら400℃まで昇温した。400℃において、水素を50Ncc/minの流量で反応器内に流通させながら1時間還元処理を行った。還元処理後、400℃において、流通ガスを水素から窒素に切り替え、50Ncc/minの流量で反応器内に流通させながら1.5時間前処理し、反応温度の635℃まで昇温した。635℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび水蒸気を3.0g/hの流量で全圧が0.10MPaとなるように反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが4.0h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである水蒸気の体積比VS/VOが1.9、n-へキサン気体の分圧が0.034MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表4に示す。 Example 13 Activity Evaluation: n-Hexane Decomposition Reaction The Pd / CeO 2 + Al—P / ZSM5 catalyst prepared in Catalyst Preparation Example 6 was pressed and compressed into aggregates, and the aggregates were crushed. The particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was filled with Pd / CeO 2 + Al—P / ZSM5 (2.4 g) as a catalyst, and the temperature was raised to 400 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 400 ° C., reduction treatment was performed for 1 hour while flowing hydrogen through the reactor at a flow rate of 50 Ncc / min. After the reduction treatment, at 400 ° C., the flow gas was switched from hydrogen to nitrogen, pretreatment was performed for 1.5 hours while flowing in the reactor at a flow rate of 50 Ncc / min, and the temperature was raised to the reaction temperature of 635 ° C. At 635 ° C., the nitrogen flowing through the reaction tube was stopped, and instead, the total pressure was 0.10 MPa at a flow rate of raw material n-hexane of 7.5 g / h and water vapor of 3.0 g / h. WHSV per mass of intermediate pore zeolite supplied to the reaction tube is 4.0 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 1. 9. The reaction was started under the condition that the partial pressure of n-hexane gas was 0.034 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 4 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例6で調製したAl-P/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてAl-P/ZSM5を2.2g充填し、大気圧下、窒素を50Ncc/minの流量で反応器内に流通させながら反応温度の635℃まで昇温した。635℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび水蒸気を3.0g/hの流量で全圧が0.10MPaとなるよう反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが4.0h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである水蒸気の体積比VS/VOが1.9、n-へキサン気体の分圧が0.034MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表4に示す。 [Comparative Example 6]
The Al-P / ZSM5 catalyst prepared in Catalyst Preparation Example 6 was pressed and compressed to form agglomerates. The agglomerates were crushed and sized to a particle size of 0.25 mm to 0.50 mm, and then passed through a fixed bed. The activity was evaluated by n-hexane decomposition reaction using a reaction apparatus. The reaction tube was filled with 2.2 g of Al—P / ZSM5 as a catalyst, and the temperature was raised to 635 ° C. of the reaction temperature while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 635 ° C., the nitrogen flowing through the reaction tube was stopped, and instead, the reaction was carried out so that the total pressure became 0.10 MPa at a flow rate of 7.5 g / h of raw material n-hexane and 3.0 g / h of water vapor. WHSV per mass of intermediate pore zeolite is 4.0 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 1.9 at the reaction temperature. The reaction was started under the condition that the partial pressure of n-hexane gas was 0.034 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 4 shows the yield of each product calculated based on the mass of the carbon component.
中間細孔ゼオライトであるSiO2/Al2O3モル比61のNH4 +型のMFIゼオライトを空気中500℃で4時間焼成することにより、SiO2/Al2O3モル比50のH+型のMFIゼオライト触媒(H-ZSM5)を調製した。SiO2/Al2O3モル比50のH-ZSM5(2.0g)に対して、Ptの担持量がPt原子として0.50質量%、Znの担持量がZn原子として0.30質量%となるように、塩化白金(IV)酸六水和物および塩化亜鉛(和光純薬工業社製)を適量の蒸留水に溶解させた溶液を用いてインシピエント・ウェットネス(incipient wetness)法により担持した。乾燥して得た粉末に対し、ヒドラジン一水和物(和光純薬工業社製)を蒸留水に溶解させて調製した0.13mol/Lのヒドラジン水溶液を滴下してPtを液相還元した後、蒸留水で濾過洗浄し、100℃で24時間乾燥してPt-Zn/ZSM5を調製した。得られたPt-Zn/ZSM5に85%リン酸水溶液(和光純薬工業社製)0.087gを含浸させて乾燥した後、空気中650℃で10時間焼成してP/Pt-Zn/ZSM5を調製した。 [Catalyst Preparation Example 11] Preparation of Metal-Containing Zeolite Catalyst (P / Pt-Zn / ZSM5) NH 4 + type MFI zeolite having an SiO 2 / Al 2 O 3 molar ratio of 61, which is an intermediate pore zeolite, was heated to 500 ° C in air. Was calcined for 4 hours to prepare an H + -type MFI zeolite catalyst (H-ZSM5) having a SiO 2 / Al 2 O 3 molar ratio of 50. With respect to H-ZSM5 (2.0 g) having a SiO 2 / Al 2 O 3 molar ratio of 50, the supported amount of Pt is 0.50% by mass as Pt atoms, and the supported amount of Zn is 0.30% by mass as Zn atoms. So as to be supported by an incipient wetness method using a solution obtained by dissolving platinum chloride (IV) acid hexahydrate and zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in an appropriate amount of distilled water. did. After liquid-phase reduction of Pt by adding 0.13 mol / L hydrazine aqueous solution prepared by dissolving hydrazine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in distilled water to the powder obtained by drying. Then, it was filtered and washed with distilled water and dried at 100 ° C. for 24 hours to prepare Pt—Zn / ZSM5. The obtained Pt—Zn / ZSM5 was impregnated with 0.087 g of 85% phosphoric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), dried and then calcined in air at 650 ° C. for 10 hours to obtain P / Pt—Zn / ZSM5. Was prepared.
触媒調製例11で調製したP/Pt-Zn/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてP/Pt-Zn/ZSM5(1.1g)を充填し、大気圧下、窒素を反応器内に流通させながら反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび水蒸気を0.75g/hの流量で全圧が0.10MPaとなるよう反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが6.8h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである水蒸気の体積比VS/VOが0.48、n-へキサン気体の分圧が0.068MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表5に示す。 Example 14 Activity Evaluation: n-Hexane Decomposition Reaction The P / Pt—Zn / ZSM5 catalyst prepared in Catalyst Preparation Example 11 was pressed and compressed to form aggregates, and the aggregates were crushed to 0. The particle size was adjusted to 25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow reactor. The reaction tube was filled with P / Pt—Zn / ZSM5 (1.1 g) as a catalyst, and the temperature was raised to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor under atmospheric pressure. At 650 ° C., the nitrogen flowing through the reaction tube was stopped, and instead, the reaction was carried out so that the total pressure became 0.10 MPa at a flow rate of 7.5 g / h for raw material n-hexane and 0.75 g / h for water vapor. WHSV per mass of intermediate pore zeolite is 6.8 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and the oxidizing gas water vapor is 0.48 at the reaction temperature. The reaction was started under the condition that the partial pressure of n-hexane gas was 0.068 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 5 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例11で調製したSiO2/Al2O3モル比61のH-ZSM5(2.0g)に対して、85%リン酸水溶液(和光純薬工業社製)0.087gを含浸させて乾燥した後、空気中650℃で10時間焼成してP/ZSM5を調製した。得られた粉末は加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒した後に反応に用いた。 [Comparative Example 7]
H-ZSM5 (2.0 g) having an SiO 2 / Al 2 O 3 molar ratio of 61 prepared in Catalyst Preparation Example 11 was impregnated with 0.087 g of 85% phosphoric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.). After drying, P / ZSM5 was prepared by calcining in air at 650 ° C. for 10 hours. The obtained powder was pressed and compressed into aggregates, and the aggregates were crushed and sized to a particle size of 0.25 mm to 0.50 mm and used for the reaction.
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5(5.0g)を20ml蒸留水に浸し、減圧下室温で脱気した。このゼオライト/水の混合液に対し、0.051gの塩化ヘキサアンミンルテニウム(III)を80mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、1.0g当たり330μmolのRuを含有するRu/ZSM5を調製した。 [Catalyst Preparation Example 12] Preparation of metal-containing zeolite catalyst (Ru / ZSM5) H-ZSM5 (5.0 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 was immersed in 20 ml distilled water, and the pressure was reduced. Degassed at room temperature. To this zeolite / water mixture, 0.051 g of hexaammineruthenium chloride (III) dissolved in 80 ml of distilled water was gradually added at room temperature, stirred at 50 ° C. for 2 hours, and then at room temperature for 2 hours. Stir further. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Ru / ZSM5 containing 330 μmol of Ru per 1.0 g.
γ-アルミナ(住友化学社製)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。このγ-アルミナ/水の混合液に対し、0.87gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、Al2O31.0g当たり330μmolのPdを含有するPd/Al2O3を調製した。 [Catalyst Preparation Example 13] Preparation of metal-containing zeolite catalyst (Pd / Al 2 O 3 + H-ZSM5) 10 g of γ-alumina (manufactured by Sumitomo Chemical Co., Ltd.) was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. To this γ-alumina / water mixture, a solution of 0.87 g of tetraamminepalladium (II) chloride monohydrate dissolved in 100 ml of distilled water is gradually added at room temperature and stirred at 50 ° C. for 2 hours. Then, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. After drying the residue after evaporation to dryness, and calcined for 4 hours at 500 ° C. in air, it was prepared of Pd / Al 2 O 3 containing Pd of Al 2 O 3 1.0 g per 330Myumol.
フュームドシリカ(Sigma-Aldrich社製)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。このフュームドシリカ/水の混合液に対し、0.87gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、SiO21.0g当たり330μmolのPdを含有するPd/SiO2を調製した。 [Catalyst Preparation Example 14] Preparation of metal-containing zeolite catalyst (Pd / SiO 2 + H-ZSM5) 10 g of fumed silica (manufactured by Sigma-Aldrich) was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. To this fumed silica / water mixture, a solution of 0.87 g of tetraamminepalladium (II) chloride monohydrate dissolved in 100 ml of distilled water was gradually added at room temperature, and the mixture was stirred at 50 ° C. for 2 hours. Then, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd / SiO 2 containing 330 μmol of Pd per 1.0 g of SiO 2 .
酸化ランタン(III)(和光純薬工業社製)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化ランタン(III)/水の混合液に対し、0.87gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、La2O31.0g当たり330μmolのPdを含有するPd/La2O3を調製した。 [Catalyst Preparation Example 15] Preparation of metal-containing zeolite catalyst (Pd / La 2 O 3 + H-ZSM5) 10 g of lanthanum oxide (III) (manufactured by Wako Pure Chemical Industries, Ltd.) was immersed in 100 ml of distilled water and dehydrated at room temperature under reduced pressure. I worried. A solution prepared by dissolving 0.87 g of tetraamminepalladium (II) chloride monohydrate in 100 ml of distilled water was gradually added to the lanthanum oxide (III) / water mixture at room temperature, After stirring for an hour, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. After drying the residue after evaporation to dryness, and calcined for 4 hours at 500 ° C. in air, the Pd / La 2 O 3 containing Pd of La 2 O 3 1.0 g per 330μmol was prepared.
酸化ジルコニウム(IV)(和光純薬工業社製)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化ジルコニウム(IV)/水の混合液に対し、0.87gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、ZrO21.0g当たり330μmolのPdを含有するPd/ZrO2を調製した。 [Catalyst Preparation Example 16] Preparation of metal-containing zeolite catalyst (Pd / ZrO 2 + H-ZSM5) 10 g of zirconium oxide (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. . A solution prepared by dissolving 0.87 g of tetraamminepalladium (II) chloride monohydrate in 100 ml of distilled water was gradually added to this zirconium oxide (IV) / water mixture at room temperature, After stirring for an hour, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd / ZrO 2 containing 330 μmol of Pd per 1.0 g of ZrO 2 .
炭酸ストロンチウム(和光純薬工業社製)10gと酸化チタン(IV)(添川理化学社製)5.4gを粉体のまま乳鉢を用いて十分に物理混合し、空気中1150℃で10時間焼成してSrTiO3を調製した。 [Catalyst Preparation Example 17] Preparation of metal-containing zeolite catalyst (Pd / SrTiO 3 + H-ZSM5) 10 g of strontium carbonate (manufactured by Wako Pure Chemical Industries) and 5.4 g of titanium (IV) oxide (manufactured by Soekawa Riken) The mixture was sufficiently physically mixed using a mortar and fired at 1150 ° C. in air for 10 hours to prepare SrTiO 3 .
触媒調製例12で調製したRu/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてRu/ZSM5を0.75g充填し、大気圧下、窒素を反応器内に流通させながら反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび炭酸ガスを1.9g/hの流量で全圧が0.17MPaとなるよう加圧して反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが10h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである炭酸ガスの体積比VS/VOが0.50、n-へキサン気体の分圧が0.11MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 Example 15 Activity Evaluation: n-Hexane Decomposition Reaction The Ru / ZSM5 catalyst prepared in Catalyst Preparation Example 12 was pressed and compressed into aggregates, which were crushed and 0.25 mm to 0. The particle size was adjusted to 50 mm and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow reactor. The reaction tube was charged with 0.75 g of Ru / ZSM5 as a catalyst, and the temperature was raised to 650 ° C. of the reaction temperature while flowing nitrogen through the reactor under atmospheric pressure. At 650 ° C., the nitrogen flowing through the reaction tube is stopped, and instead the raw material n-hexane is 7.5 g / h and carbon dioxide is 1.9 g / h, so that the total pressure becomes 0.17 MPa. Pressurized and supplied to the reaction tube, the WHSV per mass of intermediate pore zeolite is 10 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and the carbon dioxide gas as the oxidizing gas at the reaction temperature is The reaction was started under the conditions of 0.50 and a partial pressure of n-hexane gas of 0.11 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例13で調製したPd/Al2O3+H-ZSM5触媒について、触媒としてPd/Al2O3+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Example 16]
The Pd / Al 2 O 3 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 13 was treated in the same manner as in Example 15 except that 0.83 g of Pd / Al 2 O 3 + H—ZSM5 was charged as a catalyst. The activity was evaluated by a decomposition reaction. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例14で調製したPd/SiO2+H-ZSM5触媒について、触媒としてPd/SiO2+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Example 17]
The Pd / SiO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 14 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / SiO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例15で調製したPd/La2O3+H-ZSM5触媒について、触媒としてPd/La2O3+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Example 18]
The Pd / La 2 O 3 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 15 was treated in the same manner as in Example 15 except that 0.83 g of Pd / La 2 O 3 + H—ZSM5 was charged as a catalyst. The activity was evaluated by a decomposition reaction. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例16で調製したPd/ZrO2+H-ZSM5触媒について、触媒としてPd/ZrO2+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Example 19]
The Pd / ZrO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 16 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / ZrO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例17で調製したPd/SrTiO3+H-ZSM5触媒について、触媒としてPd/SrTiO3+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Example 20]
The Pd / SrTiO 3 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 17 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / SrTiO 3 + H—ZSM5 was charged as a catalyst. evaluated. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてH-ZSM5を0.75g充填し、大気圧下、窒素を反応器内に流通させながら反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hの流量で全圧が0.11MPaとなるよう加圧して反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが10h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである炭酸ガスの体積比VS/VOが0、n-へキサン気体の分圧が0.11MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Comparative Example 8]
The H—ZSM5 catalyst having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 was pressed and compressed into aggregates, and the aggregates were crushed to obtain a particle diameter of 0.25 mm to 0.50 mm. And the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was charged with 0.75 g of H-ZSM5 as a catalyst and heated to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor at atmospheric pressure. At 650 ° C., the nitrogen flowing through the reaction tube was stopped, and instead, the raw material n-hexane was pressurized to a total pressure of 0.11 MPa at a flow rate of 7.5 g / h and supplied to the reaction tube. WHSV per mass of intermediate pore zeolite is 10 h −1 , volume ratio V S / V O of n-hexane gas as raw material and carbon dioxide gas as oxidizing gas at reaction temperature is 0, and fraction of n-hexane gas The reaction was started under the condition of a pressure of 0.11 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例12で調製したRu/ZSM5触媒について、触媒としてRu/ZSM5を0.75g充填し、炭酸ガスを供給せず、全圧を0.11MPaとした以外は実施例15と同様にして、中間細孔ゼオライト質量当たりのWHSVが10h-1、VS/VOが0の条件でn-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Comparative Example 9]
About Ru / ZSM5 catalyst prepared in Catalyst Preparation Example 12, 0.75 g of Ru / ZSM5 was charged as a catalyst, carbon dioxide gas was not supplied, and the total pressure was set to 0.11 MPa. WHSV per intermediate pore zeolites mass 10h -1, and activity evaluation by hexane decomposition reaction to n- under the condition of V S / V O is 0. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてH-ZSM5を0.75g充填し、大気圧下、窒素を反応器内に流通させながら反応温度の650℃まで昇温した。650℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび炭酸ガスを1.9g/hの流量で全圧が0.17MPaとなるよう加圧して反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが10h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである炭酸ガスの体積比VS/VOが0.50、n-へキサン気体の分圧が0.11MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表6に示す。 [Comparative Example 10]
The H—ZSM5 catalyst having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 was pressed and compressed into aggregates, and the aggregates were crushed to obtain a particle diameter of 0.25 mm to 0.50 mm. And the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was charged with 0.75 g of H-ZSM5 as a catalyst and heated to a reaction temperature of 650 ° C. while flowing nitrogen through the reactor at atmospheric pressure. At 650 ° C., the nitrogen flowing through the reaction tube is stopped, and instead the raw material n-hexane is 7.5 g / h and carbon dioxide is 1.9 g / h, so that the total pressure becomes 0.17 MPa. Pressurized and supplied to the reaction tube, the WHSV per mass of intermediate pore zeolite is 10 h −1 , and the volume ratio V S / V O of the raw material n-hexane gas and the carbon dioxide gas as the oxidizing gas at the reaction temperature is The reaction was started under the conditions of 0.50 and a partial pressure of n-hexane gas of 0.11 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 6 shows the yield of each product calculated based on the mass of the carbon component.
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5(2.5g)および酸化セリウム(IV)0.25gを粉体のまま乳鉢を用いて十分に物理混合し、CeO2+H-ZSM5を調製した。 [Comparative Example 11]
H—ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and 0.25 g of cerium (IV) oxide were sufficiently physically mixed using a mortar while maintaining the powder, and CeO 2 + H-ZSM5 was prepared.
酸化セリウム(IV)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、0.17gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、CeO21.0g当たり66μmolのPdを含有するPd/CeO2を調製した。 [Catalyst Preparation Example 18] Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + H-ZSM5) 10 g of cerium (IV) oxide was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. A solution prepared by dissolving 0.17 g of tetraamminepalladium (II) chloride monohydrate in 100 ml of distilled water was gradually added to the cerium (IV) oxide / water mixture at room temperature, After stirring for an hour, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd / CeO 2 containing 66 μmol of Pd per 1.0 g of CeO 2 .
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5(2.5g)および触媒調製例2で調製したPd/CeO20.25gを粉体のまま乳鉢を用いて十分に物理混合し、ゼオライト1.0g当たり33μmolのPdを含有するPd/CeO2+H-ZSM5を調製した。 [Catalyst Preparation Example 19] Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + H-ZSM5) H-ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and a catalyst preparation example Pd / CeO 2 0.25 g prepared in 2 was sufficiently physically mixed using a mortar in the form of powder to prepare Pd / CeO 2 + H-ZSM5 containing 33 μmol of Pd per 1.0 g of zeolite.
酸化セリウム(IV)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、1.7gのテトラアンミンパラジウム(II)塩化物一水和物を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、CeO21.0g当たり660μmolのPdを含有するPd/CeO2を調製した。 [Catalyst Preparation Example 20] Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + H-ZSM5) 10 g of cerium (IV) oxide was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. A solution prepared by dissolving 1.7 g of tetraamminepalladium (II) chloride monohydrate in 100 ml of distilled water was gradually added to this cerium (IV) oxide / water mixture at room temperature, and 2% at 50 ° C. After stirring for an hour, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Pd / CeO 2 containing 660 μmol of Pd per 1.0 g of CeO 2 .
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5(2.5g)および触媒調製例1で調製したRu/CeO20.25gを粉体のまま乳鉢を用いて十分に物理混合し、ゼオライト1.0g当たり33μmolのRuを含有するRu/CeO2+H-ZSM5を調製した。 [Catalyst Preparation Example 21] Preparation of metal-containing zeolite catalyst (Ru / CeO 2 + H-ZSM5) H-ZSM5 (2.5 g) having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 and a catalyst preparation example Ru / CeO 2 ( 0.25 g) prepared in 1 was sufficiently physically mixed using a mortar in the form of powder to prepare Ru / CeO 2 + H-ZSM5 containing 33 μmol of Ru per 1.0 g of zeolite.
酸化セリウム(IV)10gを100mlの蒸留水に浸し、減圧下室温で脱気した。この酸化セリウム(IV)/水の混合液に対し、0.96gの硝酸ロジウム(III)(関東化学社製)を100mlの蒸留水に溶解した溶液を室温で徐々に添加し、50℃で2時間撹拌した後、室温で2時間さらに撹拌した。得られた混合液を、エバポレーターを用いて50℃水浴で加熱しながら減圧下で蒸発乾固させた。蒸発乾固後の残渣を乾燥後、空気中500℃で4時間焼成し、CeO21.0g当たり330μmolのRhを含有するRh/CeO2を調製した。 [Catalyst Preparation Example 22] Preparation of metal-containing zeolite catalyst (Rh / CeO 2 + H-ZSM5) 10 g of cerium (IV) oxide was immersed in 100 ml of distilled water and deaerated at room temperature under reduced pressure. A solution prepared by dissolving 0.96 g of rhodium (III) nitrate (manufactured by Kanto Chemical Co., Inc.) in 100 ml of distilled water was gradually added to the cerium (IV) oxide / water mixture at room temperature, After stirring for an hour, the mixture was further stirred at room temperature for 2 hours. The resulting mixture was evaporated to dryness under reduced pressure while heating in a 50 ° C. water bath using an evaporator. The residue after evaporation to dryness was dried and then calcined in air at 500 ° C. for 4 hours to prepare Rh / CeO 2 containing 330 μmol of Rh per 1.0 g of CeO 2 .
触媒調製例12で調製したRu/ZSM5(2.5g)および触媒調製例2で調製したPd/CeO20.25gを粉体のまま乳鉢を用いて十分に物理混合し、ゼオライト1.0g当たり33μmolのPdおよび33μmolのRuを含有するPd/CeO2+Ru/ZSM5を調製した。 [Catalyst Preparation Example 23] Preparation of metal-containing zeolite catalyst (Pd / CeO 2 + Ru / ZSM5) Ru / ZSM5 (2.5 g) prepared in Catalyst Preparation Example 12 and Pd / CeO 2 prepared in Catalyst Preparation Example 2 25 g of the powder was sufficiently physically mixed using a mortar to prepare Pd / CeO 2 + Ru / ZSM5 containing 33 μmol of Pd and 33 μmol of Ru per 1.0 g of zeolite.
触媒調製例18で調製したゼオライト1.0g当たり6.6μmolのPdを含有するPd/CeO2+H-ZSM5触媒について、触媒としてPd/CeO2+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表7に示す。 [Example 21]
Example 15 except that Pd / CeO 2 + H—ZSM5 catalyst containing 6.6 μmol of Pd per 1.0 g of the zeolite prepared in Catalyst Preparation Example 18 was charged with 0.83 g of Pd / CeO 2 + H—ZSM5 as a catalyst. In the same manner as described above, the activity was evaluated by n-hexane decomposition reaction. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例19で調製したゼオライト1.0g当たり33μmolのPdを含有するPd/CeO2+H-ZSM5触媒について、触媒としてPd/CeO2+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表7に示す。 [Example 22]
A Pd / CeO 2 + H—ZSM5 catalyst containing 33 μmol of Pd per 1.0 g of the zeolite prepared in Catalyst Preparation Example 19 was the same as Example 15 except that 0.83 g of Pd / CeO 2 + H—ZSM5 was charged as a catalyst. Then, the activity was evaluated by n-hexane decomposition reaction. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例20で調製したゼオライト1.0g当たり66μmolのPdを含有するPd/CeO2+H-ZSM5触媒について、触媒としてPd/CeO2+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表7に示す。 [Example 23]
A Pd / CeO 2 + H—ZSM5 catalyst containing 66 μmol of Pd per 1.0 g of the zeolite prepared in Catalyst Preparation Example 20 was the same as Example 15 except that 0.83 g of Pd / CeO 2 + H—ZSM5 was charged as a catalyst. Then, the activity was evaluated by n-hexane decomposition reaction. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例21で調製したRu/CeO2+H-ZSM5触媒について、触媒としてRu/CeO2+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表7に示す。 [Example 24]
The Ru / CeO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 21 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Ru / CeO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例22で調製したRh/CeO2+H-ZSM5触媒について、触媒としてRh/CeO2+H-ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表7に示す。 [Example 25]
The Rh / CeO 2 + H—ZSM5 catalyst prepared in Catalyst Preparation Example 22 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Rh / CeO 2 + H—ZSM5 was charged as a catalyst. evaluated. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例23で調製したPd/CeO2+Ru/ZSM5触媒について、触媒としてPd/CeO2+Ru/ZSM5を0.83g充填した以外は実施例15と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表7に示す。 [Example 26]
The Pd / CeO 2 + Ru / ZSM5 catalyst prepared in Catalyst Preparation Example 23 was activated by n-hexane decomposition reaction in the same manner as in Example 15 except that 0.83 g of Pd / CeO 2 + Ru / ZSM5 was charged as a catalyst. evaluated. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例19で調製したゼオライト1.0g当たり33μmolのPdを含有するPd/CeO2+H-ZSM5触媒について、触媒としてPd/CeO2+H-ZSM5を0.83g充填した以外は比較例9と同様にして、n-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表7に示す。 [Comparative Example 12]
A Pd / CeO 2 + H—ZSM5 catalyst containing 33 μmol of Pd per 1.0 g of the zeolite prepared in Catalyst Preparation Example 19 was the same as Comparative Example 9 except that 0.83 g of Pd / CeO 2 + H—ZSM5 was charged as a catalyst. Then, the activity was evaluated by n-hexane decomposition reaction. Table 7 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例11で調製したSiO2/Al2O3モル比50のH-ZSM5(2.0g)に対して、Ptの担持量がPt原子として0.50質量%、Ceの担持量がCe原子として0.30質量%となるように、塩化白金(IV)酸六水和物および硝酸セリウム(III)六水和物(和光純薬工業社製)を適量の蒸留水に溶解させた溶液を用いてインシピエント・ウェットネス(incipient wetness)法により担持した。乾燥して得た粉末に対し、ヒドラジン一水和物(和光純薬工業社製)を蒸留水に溶解させて調製した0.13mol/Lのヒドラジン水溶液を滴下してPtを液相還元した後、蒸留水で濾過洗浄し、100℃で24時間乾燥してPt-Ce/ZSM5を調製した。得られたPt-Ce/ZSM5に85%リン酸水溶液(和光純薬工業社製)0.087gを含浸させて乾燥した後、空気中650℃で10時間焼成してP/Pt-Ce/ZSM5を調製した。 [Catalyst Preparation Example 24] Preparation of Metal-Containing Zeolite Catalyst (Pd / CeO 2 + P / Pt—Ce / ZSM5) H-ZSM5 (2.0 g) having a SiO 2 / Al 2 O 3 molar ratio of 50 prepared in Catalyst Preparation Example 11 ) Platinum chloride (IV) acid hexahydrate and cerium nitrate so that the supported amount of Pt is 0.50% by mass as Pt atoms and the supported amount of Ce is 0.30% by mass as Ce atoms. (III) Hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was supported by an incipient wetness method using a solution in which an appropriate amount of distilled water was dissolved. After liquid-phase reduction of Pt by adding 0.13 mol / L hydrazine aqueous solution prepared by dissolving hydrazine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in distilled water to the powder obtained by drying. Then, it was filtered and washed with distilled water, and dried at 100 ° C. for 24 hours to prepare Pt—Ce / ZSM5. The obtained Pt—Ce / ZSM5 was impregnated with 0.087 g of 85% phosphoric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), dried and then calcined in air at 650 ° C. for 10 hours to obtain P / Pt—Ce / ZSM5. Was prepared.
触媒調製例24で調製したPd/CeO2+P/Pt-Ce/ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてPd/CeO2+P/Pt-Ce/ZSM5を1.8g充填し、大気圧下、窒素を50Ncc/minの流量で反応器内に流通させながら600℃まで昇温した。600℃において、水素を50Ncc/minの流量で反応器内に流通させながら1時間還元処理を行った。還元処理後、600℃において、流通ガスを水素から窒素に切り替え、50Ncc/minの流量で反応器内に流通させながら1.5時間前処理し、反応温度の630℃まで昇温した。630℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび炭酸ガスを7.7g/hの流量で全圧が0.11MPaとなるように反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが5.0h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである炭酸ガスの体積比VS/VOが2.0、n-へキサン気体の分圧が0.037MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表8に示す。 Example 27 Activity Evaluation: n-Hexane Decomposition Reaction The Pd / CeO 2 + P / Pt—Ce / ZSM5 catalyst prepared in Catalyst Preparation Example 24 was pressed and compressed into aggregates, and the aggregates were crushed Then, the particle size was adjusted to 0.25 mm to 0.50 mm, and the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was filled with 1.8 g of Pd / CeO 2 + P / Pt—Ce / ZSM5 as a catalyst, and the temperature was raised to 600 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 600 ° C., reduction treatment was performed for 1 hour while flowing hydrogen through the reactor at a flow rate of 50 Ncc / min. After the reduction treatment, at 600 ° C., the flow gas was switched from hydrogen to nitrogen, pretreatment was performed for 1.5 hours while flowing in the reactor at a flow rate of 50 Ncc / min, and the temperature was raised to the reaction temperature of 630 ° C. At 630 ° C., the nitrogen flowing through the reaction tube is stopped, and instead the raw material n-hexane is 7.5 g / h and carbon dioxide gas is 7.7 g / h so that the total pressure becomes 0.11 MPa. WHSV per mass of intermediate pore zeolite is 5.0 h −1 , and the volume ratio V S / V O of n-hexane gas as a raw material and carbon dioxide gas as an oxidizing gas at the reaction temperature is The reaction was started under the condition that the partial pressure of the 2.0, n-hexane gas was 0.037 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 8 shows the yield of each product calculated based on the mass of the carbon component.
触媒調製例24で調製したPd/CeO2+P/Pt-Ce/ZSM5触媒について、炭酸ガス供給量を11g/h、全圧を0.11MPaとした以外は実施例27と同様にして、中間細孔ゼオライト質量当たりのWHSVが10h-1、VS/VOが3.0、n-へキサン気体の分圧が0.028MPaの条件でn-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表8に示す。 [Example 28]
For the Pd / CeO 2 + P / Pt—Ce / ZSM5 catalyst prepared in Catalyst Preparation Example 24, the same procedure as in Example 27 was performed except that the carbon dioxide supply rate was 11 g / h and the total pressure was 0.11 MPa. The activity was evaluated by n-hexane decomposition reaction under the conditions of WHSV per pore zeolite mass of 10 h −1 , V S / V O of 3.0, and partial pressure of n-hexane gas of 0.028 MPa. Table 8 shows the yield of each product calculated based on the mass of the carbon component.
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5触媒について、加圧・圧縮して凝集塊とし、この凝集塊を破砕して0.25mm~0.50mmの粒径に整粒し、固定床流通式反応装置を用いたn-へキサン分解反応により活性評価した。反応管に触媒としてH-ZSM5を1.5g充填し、大気圧下、窒素を50Ncc/minの流量で反応器内に流通させながら反応温度の630℃まで昇温した。630℃において、反応管に流通させていた窒素を止め、代わりに原料のn-へキサンを7.5g/hおよび炭酸ガスを7.7g/hの流量で全圧が0.11MPaとなるように反応管に供給し、中間細孔ゼオライト質量当たりのWHSVが5.0h-1、反応温度における原料であるn-へキサン気体と酸化性ガスである炭酸ガスの体積比VS/VOが2.0、n-へキサン気体の分圧が0.037MPaの条件で反応を開始した。反応開始後、所定の時間が経過したところで反応生成物を直接ガスクロマトグラフ(検出器:FID)に導入し、生成物の組成を分析した。炭素成分の質量をベースとして算出した各生成物の収率を表8に示す。 [Comparative Example 13]
The H—ZSM5 catalyst having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1 was pressed and compressed into aggregates, and the aggregates were crushed to obtain a particle diameter of 0.25 mm to 0.50 mm. And the activity was evaluated by n-hexane decomposition reaction using a fixed bed flow type reactor. The reaction tube was filled with 1.5 g of H-ZSM5 as a catalyst, and the temperature was raised to a reaction temperature of 630 ° C. while flowing nitrogen through the reactor at a flow rate of 50 Ncc / min at atmospheric pressure. At 630 ° C., the nitrogen flowing through the reaction tube is stopped, and instead the raw material n-hexane is 7.5 g / h and carbon dioxide gas is 7.7 g / h so that the total pressure becomes 0.11 MPa. WHSV per mass of intermediate pore zeolite is 5.0 h −1 , and the volume ratio V S / V O of n-hexane gas as a raw material and carbon dioxide gas as an oxidizing gas at the reaction temperature is The reaction was started under the condition that the partial pressure of the 2.0, n-hexane gas was 0.037 MPa. The reaction product was directly introduced into a gas chromatograph (detector: FID) when a predetermined time had elapsed after the start of the reaction, and the composition of the product was analyzed. Table 8 shows the yield of each product calculated based on the mass of the carbon component.
比較例1で調製したSiO2/Al2O3モル比500のH-ZSM5触媒について、炭酸ガス供給量を11g/h、全圧を0.11MPaとした以外は比較例13と同様にして、中間細孔ゼオライト質量当たりのWHSVが5h-1、VS/VOが3.0の条件でn-へキサン分解反応により活性評価した。炭素成分の質量をベースとして算出した各生成物の収率を表8に示す。 [Comparative Example 14]
For the H—ZSM5 catalyst having a SiO 2 / Al 2 O 3 molar ratio of 500 prepared in Comparative Example 1, the same procedure as in Comparative Example 13 was conducted except that the carbon dioxide supply rate was 11 g / h and the total pressure was 0.11 MPa. The activity was evaluated by n-hexane decomposition reaction under the conditions of WHSV per mesopore zeolite mass of 5 h -1 and V S / V O of 3.0. Table 8 shows the yield of each product calculated based on the mass of the carbon component.
Claims (23)
- 周期律表8~10族金属(X)、および四面体型TO4(TはSi原子またはAl原子を示し、Oは酸素原子を示す)ユニット10個からなる10員環構造を有する中間細孔ゼオライト(Z1)を構成要素として含む金属含有ゼオライト触媒に、1気圧での沸点が35~180℃の範囲にある飽和炭化水素類を主成分とする原料(O)および酸化性ガス(S)を接触させることを特徴とする、エチレン、プロピレンを主成分とする炭素数2~4の低級オレフィン類の製造方法。 Intermediate pore zeolite having a 10-membered ring structure consisting of 10 units of metal (X) in the periodic table and tetrahedral TO 4 (T represents Si atom or Al atom, O represents oxygen atom) unit A metal-containing zeolite catalyst containing (Z1) as a constituent element is contacted with a raw material (O) and an oxidizing gas (S) whose main components are saturated hydrocarbons having a boiling point of 35 to 180 ° C. at 1 atm. A process for producing a lower olefin having 2 to 4 carbon atoms, the main component of which is ethylene or propylene.
- 前記酸化性ガス(S)が、水蒸気および炭酸ガスから選ばれる1種以上である請求項1に記載の低級オレフィン類の製造方法。 The method for producing lower olefins according to claim 1, wherein the oxidizing gas (S) is at least one selected from water vapor and carbon dioxide.
- 前記原料(O)の接触分解反応における反応温度において、前記原料(O)の気体が占める体積(VO)に対する、前記酸化性ガス(S)の気体が占める体積(VS)の比(VS/VO)が0.01~2の範囲にある請求項1または2に記載の低級オレフィン類の製造方法。 Ratio (V S ) of the volume occupied by the gas of the oxidizing gas (S) to the volume (V O ) occupied by the gas of the raw material (O) at the reaction temperature in the catalytic cracking reaction of the raw material (O) (V The process for producing a lower olefin according to claim 1 or 2, wherein S / V O ) is in the range of 0.01 to 2.
- 前記原料(O)の接触分解反応における反応温度が500~750℃の範囲にある請求項1~3のいずれか1項に記載の低級オレフィン類の製造方法。 The method for producing a lower olefin according to any one of claims 1 to 3, wherein a reaction temperature in the catalytic cracking reaction of the raw material (O) is in the range of 500 to 750 ° C.
- 中間細孔ゼオライト(Z1)がMFI型、MWW型またはFER型の中間細孔ゼオライト(Z1’)である請求項1~4のいずれか1項に記載の低級オレフィン類の製造方法。 The method for producing lower olefins according to any one of claims 1 to 4, wherein the intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ').
- 前記金属含有ゼオライト触媒が、周期律表3族元素(Y1)および周期律表15族元素(Y2)からなる群から選ばれる1種以上の元素を構成要素としてさらに含み、
前記元素(Y2)は、P、As、SbおよびBiから選ばれる1種以上の元素である請求項1~5のいずれか1項に記載の低級オレフィン類の製造方法。 The metal-containing zeolite catalyst further contains one or more elements selected from the group consisting of Group 3 elements (Y1) and Periodic table 15 elements (Y2) as a constituent element,
The method for producing a lower olefin according to any one of claims 1 to 5, wherein the element (Y2) is one or more elements selected from P, As, Sb and Bi. - 前記金属含有ゼオライト触媒が、前記元素(Y2)を含み、
前記元素(Y2)がPである請求項6に記載の低級オレフィン類の製造方法。 The metal-containing zeolite catalyst contains the element (Y2);
The method for producing a lower olefin according to claim 6, wherein the element (Y2) is P. - 前記金属含有ゼオライト触媒が、前記元素(Y1)を含み、
前記元素(Y1)がCeである請求項6または7に記載の低級オレフィン類の製造方法。 The metal-containing zeolite catalyst contains the element (Y1),
The method for producing lower olefins according to claim 6 or 7, wherein the element (Y1) is Ce. - 前記中間細孔ゼオライト(Z1)がMFI型、MWW型またはFER型の中間細孔ゼオライト(Z1’)であり、前記中間細孔ゼオライト(Z1’)に前記金属(X)が担持されている請求項5~8のいずれか1項に記載の低級オレフィン類の製造方法。 The intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′), and the metal (X) is supported on the intermediate pore zeolite (Z1 ′). Item 9. The method for producing a lower olefin according to any one of Items 5 to 8.
- 前記中間細孔ゼオライト(Z1’)に周期律表3族元素(Y1)および周期律表15族元素(Y2)からなる群から選ばれる1種以上の元素がさらに担持され、
前記元素(Y2)は、P、As、SbおよびBiから選ばれる1種以上の元素である請求項9に記載の低級オレフィン類の製造方法。 One or more elements selected from the group consisting of Group 3 elements (Y1) and Periodic table 15 elements (Y2) of the periodic table are further supported on the intermediate pore zeolite (Z1 ′),
The method for producing a lower olefin according to claim 9, wherein the element (Y2) is one or more elements selected from P, As, Sb, and Bi. - 前記中間細孔ゼオライト(Z1)がMFI型、MWW型またはFER型の中間細孔ゼオライト(Z1’)であり、
金属含有ゼオライト触媒が、前記元素(Y1)の酸化物(Z2)に担持されている前記金属(X)、または前記中間細孔ゼオライト(Z1’)および前記酸化物(Z2)のいずれとも異なる無機固体化合物(Z3)に担持されている前記金属(X)と、前記中間細孔ゼオライト(Z1’)との物理混合体である請求項6~8のいずれか1項に記載の低級オレフィン類の製造方法。 The intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′),
The metal-containing zeolite catalyst is an inorganic material different from the metal (X) supported on the oxide (Z2) of the element (Y1), or the intermediate pore zeolite (Z1 ′) and the oxide (Z2). The lower olefins according to any one of claims 6 to 8, which is a physical mixture of the metal (X) supported on the solid compound (Z3) and the intermediate pore zeolite (Z1 '). Production method. - 前記中間細孔ゼオライト(Z1)がMFI型、MWW型またはFER型の中間細孔ゼオライト(Z1’)であり、
金属含有ゼオライト触媒が、前記元素(Y1)の酸化物(Z2)に担持されている前記金属(X)、または前記中間細孔ゼオライト(Z1’)および前記酸化物(Z2)のいずれとも異なる無機固体化合物(Z3)に担持されている前記金属(X)と、前記元素(Y2)が担持されている前記中間細孔ゼオライト(Z1’)との物理混合体である請求項6~8のいずれか1項に記載の低級オレフィン類の製造方法。 The intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′),
The metal-containing zeolite catalyst is an inorganic material different from the metal (X) supported on the oxide (Z2) of the element (Y1), or the intermediate pore zeolite (Z1 ′) and the oxide (Z2). The physical mixture of the metal (X) supported on the solid compound (Z3) and the intermediate pore zeolite (Z1 ') supported on the element (Y2). A process for producing the lower olefin according to claim 1. - 前記中間細孔ゼオライト(Z1’)にAlがさらに担持されている請求項12に記載の低級オレフィン類の製造方法。 The method for producing lower olefins according to claim 12, wherein Al is further supported on the intermediate pore zeolite (Z1 ').
- 金属含有ゼオライト触媒は、前記元素(Y2)としてPを必須元素として含み、前記中間細孔ゼオライト(Z1’)に担持されるAlが、ベーマイト、擬ベーマイト、アルミナ、アルミニウム塩、および非晶質シリカ-アルミナから選ばれる少なくとも一つのアルミニウム含有化合物(A)に由来する請求項13に記載の低級オレフィン類の製造方法。 The metal-containing zeolite catalyst contains P as an essential element as the element (Y2), and Al supported on the intermediate pore zeolite (Z1 ′) is boehmite, pseudoboehmite, alumina, aluminum salt, and amorphous silica. The method for producing lower olefins according to claim 13, derived from at least one aluminum-containing compound (A) selected from alumina.
- 前記アルミニウム含有化合物(A)がベーマイトまたは擬ベーマイトのいずれかである請求項14に記載の低級オレフィン類の製造方法。 The method for producing a lower olefin according to claim 14, wherein the aluminum-containing compound (A) is either boehmite or pseudoboehmite.
- 前記中間細孔ゼオライト(Z1’)に含まれるSiおよびAlの組成が、シリカとアルミナに換算したモル比(SiO2/Al2O3)で30~100の範囲にあり、かつ、前記金属含有ゼオライト触媒に含まれるAl成分の合計がAl原子として、1~10質量%の範囲にある請求項13~15のいずれか1項に記載の低級オレフィン類の製造方法。 The composition of Si and Al contained in the intermediate pore zeolite (Z1 ′) is in a range of 30 to 100 in terms of a molar ratio (SiO 2 / Al 2 O 3 ) converted to silica and alumina, and the metal-containing The method for producing lower olefins according to any one of claims 13 to 15, wherein the total of Al components contained in the zeolite catalyst is in the range of 1 to 10% by mass as Al atoms.
- 前記金属含有ゼオライト触媒に含まれるPおよびAlの組成が、原子モル比(P/Al)で0.1~1.0の範囲である請求項14~16のいずれか1項に記載の低級オレフィン類の製造方法。 The lower olefin according to any one of claims 14 to 16, wherein the composition of P and Al contained in the metal-containing zeolite catalyst is in the range of 0.1 to 1.0 in terms of atomic molar ratio (P / Al). Manufacturing method.
- 前記酸化物(Z2)が酸化セリウムである請求項11~17のいずれか1項に記載の低級オレフィン類の製造方法。 The method for producing a lower olefin according to any one of claims 11 to 17, wherein the oxide (Z2) is cerium oxide.
- 前記無機固体化合物(Z3)がペロブスカイト化合物である請求項11~18のいずれか1項に記載の低級オレフィン類の製造方法。 The method for producing a lower olefin according to any one of claims 11 to 18, wherein the inorganic solid compound (Z3) is a perovskite compound.
- 前記中間細孔ゼオライト(Z1)がMFI型、MWW型またはFER型の中間細孔ゼオライト(Z1’)であり、
金属含有ゼオライト触媒が、前記元素(Y1)の酸化物(Z2)に担持されている前記金属(X)、または前記中間細孔ゼオライト(Z1’)および前記酸化物(Z2)のいずれとも異なる無機固体化合物(Z3)に担持されている前記金属(X)と、前記中間細孔ゼオライト(Z1’)に担持されている前記金属(X)との物理混合体である請求項6~8のいずれか1項に記載の低級オレフィン類の製造方法。 The intermediate pore zeolite (Z1) is an MFI type, MWW type or FER type intermediate pore zeolite (Z1 ′),
The metal-containing zeolite catalyst is an inorganic material different from the metal (X) supported on the oxide (Z2) of the element (Y1), or the intermediate pore zeolite (Z1 ′) and the oxide (Z2). 9. The physical mixture of the metal (X) supported on the solid compound (Z3) and the metal (X) supported on the intermediate pore zeolite (Z1 ′). A process for producing the lower olefin according to claim 1. - 前記中間細孔ゼオライト(Z1’)に前記元素(Y1)及び前記元素(Y2)から選ばれる1種以上の元素がさらに担持されている請求項20に記載の低級オレフィン類の製造方法。 The method for producing lower olefins according to claim 20, wherein the intermediate pore zeolite (Z1 ') further carries one or more elements selected from the element (Y1) and the element (Y2).
- 前記中間細孔ゼオライト(Z1’)にAlがさらに担持されている請求項10に記載の低級オレフィン類の製造方法。 The method for producing lower olefins according to claim 10, wherein Al is further supported on the intermediate pore zeolite (Z1 ').
- 前記金属(X)がRu、Rh、Ir、Ni、PdおよびPtから選ばれる金属である請求項1~22のいずれか1項に記載の低級オレフィン類の製造方法。 The method for producing a lower olefin according to any one of claims 1 to 22, wherein the metal (X) is a metal selected from Ru, Rh, Ir, Ni, Pd and Pt.
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JP2016175038A (en) * | 2015-03-20 | 2016-10-06 | 三菱化学株式会社 | Zeolite molding |
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JP2007531620A (en) * | 2004-04-02 | 2007-11-08 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Catalyst composition comprising metal phosphate bonded zeolite and method of use for catalytic cracking of hydrocarbons |
JP2007050404A (en) * | 2005-08-15 | 2007-03-01 | China Petrochemical Corp | Fluid-bed catalyst for preparation of ethylene and propylene by catalytic cracking |
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JP6259455B2 (en) | 2018-01-10 |
CN105308009A (en) | 2016-02-03 |
KR20160018677A (en) | 2016-02-17 |
CN105308009B (en) | 2018-04-20 |
KR101800558B1 (en) | 2017-11-22 |
JPWO2014196211A1 (en) | 2017-02-23 |
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